Composite oxide semiconductor and transistor

ABSTRACT

A novel material is provided. A composite oxide semiconductor includes a first region and a second region. The first region contains indium. The second region contains an element M (the element M is one or more of Ga, Al, Hf, Y, and Sn). The first region and the second region are arranged in a mosaic pattern. The composite oxide semiconductor further includes a third region. The element M is gallium. The first region contains indium oxide or indium zinc oxide. The second region contains gallium oxide or gallium zinc oxide. The third region contains zinc oxide.

TECHNICAL FIELD

The present invention relates to an object, a method, or a manufacturingmethod. The present invention relates to a process, a machine,manufacture, or a composition of matter. One embodiment of the presentinvention particularly relates to an oxide semiconductor or amanufacturing method of the oxide semiconductor. One embodiment of thepresent invention relates to a semiconductor device, a display device, aliquid crystal display device, a light-emitting device, a power storagedevice, a memory device, a method for driving them, or a method formanufacturing them.

In this specification and the like, a semiconductor device generallymeans a device that can function by utilizing semiconductorcharacteristics. A semiconductor element such as a transistor, asemiconductor circuit, an arithmetic device, and a memory device areeach an embodiment of a semiconductor device. An imaging device, adisplay device, a liquid crystal display device, a light-emittingdevice, an electro-optical device, a power generation device (includinga thin film solar cell, an organic thin film solar cell, and the like),and an electronic appliance may each include a semiconductor device.

BACKGROUND ART

Non-Patent Document 1 discloses a solid solution range in theIn₂O₃—Ga₂ZnO₄—ZnO system.

Furthermore, a technique in which a transistor is fabricated using anIn—Ga—Zn-based oxide semiconductor is disclosed (for example, see PatentDocument 1).

Non-Patent Document 2 discusses a structure where an oxide semiconductorconsisting of a dual-layer stack of indium zinc oxide and IGZO is usedas an active layer of a transistor.

REFERENCE Patent Document

-   [Patent Document 1] Japanese Published Patent Application No.    2007-96055

Non-Patent Documents

-   [Non-Patent Document 1] M. Nakamura, N. Kimizuka, and T. Mohri, “The    Phase Relations in the In₂O₃—Ga₂ZnO₄—ZnO System at 1350° C.”, J.    Solid State Chem., 1991, Vol. 93, pp. 298-315.-   [Non-Patent Document 2] John F. Wager, “Oxide TFTs: A Progress    Report”, Information Display 1/16, SID 2016, January/February 2016,    Vol. 32, No. 1, pp. 16-21.

DISCLOSURE OF INVENTION

In Non-Patent Document 2, a channel-protective bottom-gate transistorachieves high field-effect mobility (μ=62 cm² V⁻¹s⁻¹). An active layerof the transistor is a dual-layer stack of indium zinc oxide and IGZO,and the thickness of the indium zinc oxide where a channel is formed is10 nm. However, the S value (the subthreshold swing (SS)), which is oneof transistor characteristics, is as large as 0.41 V/decade. Moreover,the threshold voltage (V_(th)), which is also one of transistorcharacteristics, is −2.9 V, which means that the transistor has anormally-on characteristic.

In view of the above problem, an object of one embodiment of the presentinvention is to provide a novel oxide semiconductor. Another object isto give favorable electrical characteristics to a semiconductor device.Another object of the present invention is to provide a highly reliablesemiconductor device. Another object is to provide a semiconductordevice with a novel structure. Another object is to provide a displaydevice with a novel structure.

Note that the descriptions of these objects do not disturb the existenceof other objects. In one embodiment of the present invention, there isno need to achieve all the objects. Other objects will be apparent fromand can be derived from the description of the specification, thedrawings, the claims, and the like.

One embodiment of the present invention is a composite oxidesemiconductor including a first region and a second region. The firstregion contains indium. The second region contains an element M (theelement M is one or more of Ga, Al, Hf, Y, and Sn). The first region andthe second region are arranged in a mosaic pattern.

The composite oxide semiconductor having the above composition furtherincludes a third region. The element M is gallium. The first regioncontains indium oxide or indium zinc oxide. The second region containsgallium oxide or gallium zinc oxide. The third region contains zincoxide.

In the above composition, the first region, the second region, or thethird region has a blurred periphery and a cloud-like composition.

In the composite oxide semiconductor having the above composition, adiameter of the second region is greater than or equal to 0.5 nm andless than or equal to 10 nm, or a neighborhood thereof.

In the composite oxide semiconductor having the above composition, adiameter of the second region is greater than or equal to 1 nm and lessthan or equal to 2 nm, or a neighborhood thereof.

In the composite oxide semiconductor having the above composition, anatomic ratio of the indium to the gallium and the zinc is 4:2:3 or aneighborhood thereof.

In the composite oxide semiconductor having the above composition, anatomic ratio of the indium to the gallium and the zinc is 5:1:6 or aneighborhood thereof.

In the composite oxide semiconductor having the above composition, anatomic ratio of the indium to the gallium and the zinc is 1:1:1 or aneighborhood thereof.

Another embodiment of the present invention is a transistor includingthe composite oxide semiconductor having the above composition.

According to one embodiment of the present invention, a novel oxidesemiconductor can be provided. According to one embodiment of thepresent invention, a semiconductor device can be provided with favorableelectrical characteristics. A highly reliable semiconductor device canbe provided. A semiconductor device with a novel structure can beprovided. A display device with a novel structure can be provided.

Note that the description of these effects does not preclude theexistence of other effects. One embodiment of the present invention doesnot necessarily achieve all the effects listed above. Other effects willbe apparent from and can be derived from the description of thespecification, the drawings, the claims, and the like.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings:

FIG. 1 is a conceptual diagram of a composition of an oxidesemiconductor;

FIG. 2 is a conceptual diagram of a composition of an oxidesemiconductor;

FIGS. 3A to 3C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 4A to 4C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 5A and 5B are cross-sectional views illustrating a semiconductordevice;

FIGS. 6A to 6D are cross-sectional views illustrating a method formanufacturing a semiconductor device;

FIGS. 7A to 7C are cross-sectional views illustrating a method formanufacturing a semiconductor device;

FIGS. 8A to 8C are cross-sectional views illustrating a method formanufacturing a semiconductor device;

FIGS. 9A to 9C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 10A to 10C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 11A to 11C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 12A to 12C are a top view and cross-sectional views illustrating asemiconductor device;

FIGS. 13A to 13C each illustrate an atomic ratio range of an oxidesemiconductor of the present invention;

FIG. 14 shows measurement results of XRD spectra of samples of Example;

FIGS. 15A to 15F show cross-sectional TEM images and electrondiffraction patterns of samples of Example;

FIGS. 16A to 16L show a plan-view TEM image, a cross-sectional TEMimage, and electron diffraction patterns of a sample of Example;

FIG. 17 shows plan-view TEM images of samples of Example and imagesobtained through analysis thereof;

FIGS. 18A to 18D illustrate a method for deriving a rotation angle of ahexagon;

FIGS. 19A to 19E illustrate a method for forming a Voronoi diagram;

FIG. 20 shows the number and proportions of shapes of Voronoi regions ofExample;

FIGS. 21A to 21H show a plan-view TEM image, a cross-sectional TEMimage, and EDX mapping images of a sample of Example;

FIGS. 22A to 22C show EDX mapping images of a sample of Example;

FIG. 23 shows I_(d)-V_(g) curves of samples of Example;

FIG. 24 shows I_(d)-V_(g) characteristics of samples of Example after+GBT stress tests;

FIGS. 25A to 25F show cross-sectional TEM images and electrondiffraction patterns of samples of Example;

FIGS. 26A to 26F show plan-view TEM images of samples of Example andimages obtained through analysis thereof;

FIGS. 27A to 27C show the number and proportions of shapes of Voronoiregions of Example;

FIGS. 28A to 28H show a plan-view TEM image, a cross-sectional TEMimage, and EDX mapping images of a sample of Example;

FIGS. 29A to 29C show EDX mapping images of a sample of Example; and

FIG. 30 shows I_(d)-V_(g) curves of samples of Example.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments will be described with reference to drawings.However, the embodiments can be implemented with various modes. It willbe readily appreciated by those skilled in the art that modes anddetails can be changed in various ways without departing from the spiritand scope of the present invention. Thus, the present invention shouldnot be interpreted as being limited to the following description of theembodiments.

In the drawings, the size, the layer thickness, or the region isexaggerated for clarity in some cases. Therefore, the size, the layerthickness, or the region is not limited to the illustrated scale. Notethat the drawings are schematic views showing ideal examples, andembodiments of the present invention are not limited to shapes or valuesshown in the drawings.

Note that in this specification, ordinal numbers such as “first”,“second”, and “third” are used in order to avoid confusion amongcomponents, and the terms do not limit the components numerically.

In this specification, terms for describing arrangement, such as “over”,“above”, “under”, and “below”, are used for convenience in describing apositional relation between components with reference to drawings.Furthermore, the positional relation between components is changed asappropriate in accordance with a direction in which each component isdescribed. Thus, there is no limitation on terms used in thisspecification, and description can be made appropriately depending onthe situation.

In this specification and the like, a transistor is an element having atleast three terminals of a gate, a drain, and a source. The transistorhas a channel region between a drain (a drain terminal, a drain region,or a drain electrode) and a source (a source terminal, a source region,or a source electrode), and current can flow between the source and thedrain through the channel region. Note that in this specification andthe like, a channel region refers to a region through which currentmainly flows.

Furthermore, functions of a source and a drain might be switched whentransistors having different polarities are employed or a direction ofcurrent flow is changed in circuit operation, for example. Therefore,the terms “source” and “drain” can be switched in this specification andthe like.

Note that in this specification and the like, the term “electricallyconnected” includes the case where components are connected through an“object having any electric function”. There is no particular limitationon the “object having any electric function” as long as electric signalscan be transmitted and received between components that are connectedthrough the object. Examples of an “object having any electric function”are a switching element such as a transistor, a resistor, an inductor, acapacitor, and an element with a variety of functions as well as anelectrode and a wiring.

In this specification and the like, a “silicon oxynitride film” refersto a film that includes oxygen at a higher proportion than nitrogen, anda “silicon nitride oxide film” refers to a film that includes nitrogenat a higher proportion than oxygen.

In the description of modes of the present invention in thisspecification and the like with reference to the drawings, the samecomponents in different drawings are commonly denoted by the samereference numeral in some cases.

In this specification and the like, the term “parallel” indicates thatthe angle formed between two straight lines is greater than or equal to−10° and less than or equal to 10°, and accordingly also includes thecase where the angle is greater than or equal to −5° and less than orequal to 5°. In addition, the term “substantially parallel” indicatesthat the angle formed between two straight lines is greater than orequal to −30° and less than or equal to 30°. In addition, the term“perpendicular” indicates that the angle formed between two straightlines is greater than or equal to 80° and less than or equal to 100°,and accordingly also includes the case where the angle is greater thanor equal to 85° and less than or equal to 95°. In addition, the term“substantially perpendicular” indicates that the angle formed betweentwo straight lines is greater than or equal to 60° and less than orequal to 120°.

In this specification and the like, the terms “film” and “layer” can beinterchanged with each other depending on the case. For example, theterm “conductive layer” can be changed into the term “conductive film”in some cases. Also, the term “insulating film” can be changed into theterm “insulating layer” in some cases.

Note that a “semiconductor” includes characteristics of an “insulator”in some cases when the conductivity is sufficiently low, for example.Furthermore, a “semiconductor” and an “insulator” cannot be strictlydistinguished from each other in some cases because a border between the“semiconductor” and the “insulator” is not clear. Accordingly, a“semiconductor” in this specification can be called an “insulator” insome cases. Similarly, an “insulator” in this specification can becalled a “semiconductor” in some cases.

Note that in this specification and the like, “In:Ga:Zn=4:2:3 or aneighborhood of In:Ga:Zn=4:2:3” refers to an atomic ratio where, when Inis 4 with respect to the total number of atoms, Ga is greater than orequal to 1 and less than or equal to 3 (1≤Ga≤3) and Zn is greater thanor equal to 2 and less than or equal to 4 (2≤Zn≤4). “In:Ga:Zn=5:1:6 or aneighborhood of In:Ga:Zn=5:1:6” refers to an atomic ratio where, when Inis 5 with respect to the total number of atoms, Ga is greater than 0.1and less than or equal to 2 (0.1<Ga≤2) and Zn is greater than or equalto 5 and less than or equal to 7 (5≤Zn≤7). “In:Ga:Zn=1:1:1 or aneighborhood of In:Ga:Zn=1:1:1” refers to an atomic ratio where, when Inis 1 with respect to the total number of atoms, Ga is greater than 0.1and less than or equal to 2 (0.1<Ga≤2) and Zn is greater than 0.1 andless than or equal to 2 (0.1<Zn≤2).

Embodiment 1

In this embodiment, an oxide semiconductor material of one embodiment ofthe present invention will be described.

Note that an oxide semiconductor material preferably contains at leastindium. In particular, indium and zinc are preferably contained. Inaddition, gallium, aluminum, yttrium, tin, or the like is preferablycontained. Furthermore, one or more elements selected from boron,silicon, titanium, iron, nickel, germanium, zirconium, molybdenum,lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium,and the like may be contained.

Here, the case where an oxide semiconductor material contains indium, anelement M, and zinc is considered. The element M is gallium, aluminum,yttrium, tin, or the like. Other elements that can be used as theelement M include boron, silicon, titanium, iron, nickel, germanium,zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum,tungsten, and magnesium. Note that two or more of the above elements maybe used in combination as the element M. Note that the terms of theatomic ratio of indium to the element M and zinc in the oxidesemiconductor are denoted by [In], [M], and [Zn], respectively.

<Composition of Oxide Semiconductor Material>

FIG. 1 and FIG. 2 are conceptual diagrams of oxide semiconductormaterials of the present invention. In this specification, an oxidesemiconductor of one embodiment of the present invention is defined as acloud-aligned composite oxide semiconductor (CAC-OS).

As illustrated in FIG. 1 , the CAC has, for example, a composition inwhich elements included in the oxide semiconductor material are unevenlydistributed, and regions 001, regions 002, and regions 003 mainlyincluding the respective elements are formed. The regions 001, 002, and003 are mixed to form a mosaic pattern. In other words, in thecomposition of the CAC-OS, materials including unevenly distributedelements each have a size of greater than or equal to 0.5 nm and lessthan or equal to 10 nm, preferably greater than or equal to 1 nm andless than or equal to 2 nm, or a similar size. Note that in thefollowing description of an oxide semiconductor, a state in which one ormore metal elements are unevenly distributed and regions including themetal element(s) are mixed is referred to as a mosaic pattern or apatch-like pattern. The region has a size of greater than or equal to0.5 nm and less than or equal to 10 nm, preferably greater than or equalto 1 nm and less than or equal to 2 nm, or a similar size.

For example, an In-M-Zn oxide with the CAC composition has a compositionin which materials are separated into indium oxide (InO_(X1), where X1is a real number greater than 0) or indium zinc oxide(In_(X2)Zn_(Y2)O_(Z2), where X2, Y2, and Z2 are real numbers greaterthan 0), and an oxide of the element M (MO_(X3), where X3 is a realnumber greater than 0) or an M-Zn oxide (M_(X4)Zn_(Y4)O_(Z4), where X4,Y4, and Z4 are real numbers greater than 0), and a mosaic pattern isformed. InO_(X1) or In_(X2)Zn_(Y2)O_(Z2) forming the mosaic pattern isuniformly distributed in the film. This composition is also referred toas a cloud-like composition.

Here, suppose that the concept of FIG. 1 is applied to an In-M-Zn oxidewith the CAC composition. In this case, it can be said that the region001 is a region including MO_(X3) as a main component, the region 002 isa region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component,and the region 003 is a region including at least Zn. Surroundingportions of the region including MO_(X3) as a main component, the regionincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component, and theregion including at least Zn are unclear (blurred), so that boundariesare not clearly observed in some cases.

That is, the In-M-Zn oxide with the CAC composition is a composite oxidesemiconductor with a composition in which a region including MO_(X3) asa main component and a region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)as a main component are mixed. Thus, the oxide semiconductor material isreferred to as a composite oxide semiconductor in some cases. Note thatin this specification, for example, when the atomic ratio of In to theelement M in the region 002 is greater than the atomic ratio of In tothe element M in the region 001, the region 002 has higher Inconcentration than the region 001.

Note that in the CAC composition, a stacked-layer structure includingtwo or more films with different atomic ratios is not included. Forexample, a two-layer structure of a film including In as a maincomponent and a film including Ga as a main component is not included.

Specifically, of In—Ga—Zn oxide (hereinafter also referred to as IGZO),CAC-IGZO is described. The CAC-IGZO is an oxide material in whichmaterials are separated into InO_(X1) or In_(X2)Zn_(Y2)O_(Z2), andgallium oxide (GaO_(X5), where X5 is a real number greater than 0) orgallium zinc oxide (Ga_(X6)Zn_(Y6)O_(Z6), where X6, Y6, and Z6 are realnumbers greater than 0), for example, and a mosaic pattern is formed.InO_(X1) or In_(X2)Zn_(Y2)O_(Z2) forming the mosaic pattern is acloud-like oxide material.

That is, the CAC-IGZO is a composite oxide semiconductor with acomposition in which a region including GaO_(X5) as a main component anda region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main componentare mixed. Surrounding portions of the region including GaO_(X5) as amain component and the region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)as a main component are unclear (blurred), so that boundaries are notclearly observed in some cases.

Note that the sizes of the regions 001 to 003 can be obtained by EDXmapping. For example, the diameter of the region 001 is greater than orequal to 0.5 nm and less than or equal to 10 nm, or greater than orequal to 1 nm and less than or equal to 2 nm in the EDX mapping image ofa cross-sectional photograph in some cases. The density of an elementwhich is a main component is gradually lowered from the central portionof the region toward the surrounding portion. For example, when thenumber (abundance) of atoms of an element countable in an EDX mappingimage gradually changes from the central portion toward the surroundingportion, the surrounding portion of the region is unclear (blurred) inthe EDX mapping of the cross-sectional photograph. For example, from thecentral portion toward the surrounding portion in the region includingGaO_(X5) as a main component, the number of Ga atoms gradually reducesand the number of Zn atoms gradually increases, so that the regionincluding Ga_(X6)Zn_(Y6)O_(Z6) as a main component gradually appears.Accordingly, the surrounding portion of the region including GaO_(X5) asa main component is unclear (blurred) in the EDX mapping image.

Here, a compound including In, Ga, Zn, and O is also known as IGZO.Typical examples of IGZO include a crystalline compound represented byInGaO₃(ZnO)_(m1) (m1 is a natural number) and a crystalline compoundrepresented by In_((1+x0))Ga_((1−x0))O₃(ZnO)_(m0) (−1≤x0≤1; m0 is agiven number).

The above crystalline compounds have a single crystal structure, apolycrystalline structure, or a c-axis-aligned crystalline (CAAC)structure. Note that the CAAC structure is a layered crystal structurein which a plurality of IGZO nanocrystals have c-axis alignment and areconnected in the a-b plane direction without alignment.

In contrast, the crystal structure is a secondary element for theCAC-IGZO. In this specification, CAC-IGZO can be defined as an oxidematerial containing In, Ga, Zn, and O in the state where a plurality ofregions including Ga as a main component and a plurality of regionsincluding In as a main component are each dispersed randomly in a mosaicpattern.

For example, in the conceptual diagram of FIG. 1 , the region 001 andthe region 002 correspond to a region including Ga as a main componentand a region including In as a main component, respectively. Inaddition, the region 003 corresponds to a region including Zn. Note thatthe region including Ga as a main component and the region including Inas a main component may each be referred to as a nanoparticle. Thediameter of the nanoparticle is greater than or equal to 0.5 nm and lessthan or equal to 10 nm, typically greater than or equal to 1 nm and lessthan or equal to 2 nm. Surrounding portions of the nanoparticles areunclear (blurred), so that a boundary is not clearly observed in somecases.

In addition, FIG. 2 is a modification example of the conceptual diagramof FIG. 1 . As shown in FIG. 2 , the shapes and densities of the regions001, 002, and 003 may change depending on formation conditions of theCAC-OS.

The crystallinity of the CAC-IGZO can be analyzed by electrondiffraction. For example, a ring-like region with high luminance isobserved in an electron diffraction pattern image. Furthermore, aplurality of spots are observed in the ring-like region in some cases.

As described above, CAC-IGZO has a structure different from that of anIGZO compound in which metal elements are evenly distributed, and hascharacteristics different from those of the IGZO compound. That is, inCAC-IGZO, regions including GaO_(X5) or the like as a main component andregions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main componentare separated to form a mosaic pattern. Accordingly, when CAC-IGZO isused for a semiconductor element, the property derived from GaO_(X5) orthe like and the property derived from In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)complement each other, whereby high on-state current (Ion), highfield-effect mobility (4 and low off-state current (I_(off)) can beachieved.

Note that the conduction mechanism of a semiconductor element includingCAC-IGZO that achieves high on-state current (Ion), high field-effectmobility (μ), and low off-state current (I_(off)) can be presumed by arandom-resistance-network model in percolation theory.

A semiconductor element including CAC-IGZO has high reliability. Thus,CAC-IGZO is suitably used in a variety of semiconductor devices typifiedby a display.

<Transistor Including Oxide Semiconductor Material>

Next, the case where the oxide material is used for an oxidesemiconductor in a transistor is described.

With the use of the oxide material in a transistor, the transistor canhave high field-effect mobility and high switching characteristics. Inaddition, the transistor can have high reliability.

A semiconductor with a low carrier density is preferably used in atransistor. For example, an oxide semiconductor whose carrier density islower than 8×10¹¹/cm³, preferably lower than 1×10¹¹/cm³, furtherpreferably lower than 1×10¹⁰/cm³, and greater than or equal to1×10⁻⁹/cm³ is used.

A highly purified intrinsic or substantially highly purified intrinsicoxide semiconductor has few carrier generation sources, and thus canhave a low carrier density. A highly purified intrinsic or substantiallyhighly purified intrinsic oxide semiconductor has a low density ofdefect states and accordingly has a low density of trap states in somecases.

Charges trapped by the trap states in the oxide semiconductor take along time to be released and may behave like fixed charges. Thus, thetransistor whose channel region is formed in the oxide semiconductorhaving a high density of trap states has unstable electricalcharacteristics in some cases.

To obtain stable electrical characteristics of the transistor, it iseffective to reduce the concentration of impurities in the oxidesemiconductor. In addition, to reduce the concentration of impurities inthe oxide semiconductor, the concentration of impurities in a film thatis adjacent to the oxide semiconductor is preferably reduced. Examplesof impurities include hydrogen, nitrogen, alkali metal, alkaline earthmetal, iron, nickel, and silicon.

Here, the influence of impurities in the oxide semiconductor will bedescribed.

When silicon or carbon that is one of Group 14 elements is contained inthe oxide semiconductor, defect states are formed. Thus, theconcentration of silicon or carbon in the oxide semiconductor and aroundan interface with the oxide semiconductor (measured by secondary ionmass spectrometry (SIMS)) is set lower than or equal to 2×10¹⁸atoms/cm³, and preferably lower than or equal to 2×10¹⁷ atoms/cm³.

When the oxide semiconductor contains alkali metal or alkaline earthmetal, defect states are formed and carriers are generated, in somecases. Thus, a transistor including an oxide semiconductor whichcontains alkali metal or alkaline earth metal is likely to benormally-on. Therefore, it is preferable to reduce the concentration ofalkali metal or alkaline earth metal in the oxide semiconductor.Specifically, the concentration of alkali metal or alkaline earth metalin the oxide semiconductor, which is measured by SIMS, is lower than orequal to 1×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁶atoms/cm³.

When the oxide semiconductor contains nitrogen, the oxide semiconductoreasily becomes n-type by generation of electrons serving as carriers andan increase of carrier density. Thus, a transistor including an oxidesemiconductor which contains nitrogen is likely to be normally-on. Forthis reason, nitrogen in the oxide semiconductor is preferably reducedas much as possible; the nitrogen concentration measured by SIMS is set,for example, lower than 5×10¹⁹ atoms/cm³, preferably lower than or equalto 5×10¹⁸ atoms/cm³, further preferably lower than or equal to 1×10¹⁸atoms/cm³, and still further preferably lower than or equal to 5×10¹⁷atoms/cm³.

Hydrogen contained in an oxide semiconductor reacts with oxygen bondedto a metal atom to be water, and thus causes an oxygen vacancy (Vo), insome cases. Due to entry of hydrogen into the oxygen vacancy (Vo), anelectron serving as a carrier is generated in some cases. Furthermore,in some cases, bonding of part of hydrogen to oxygen bonded to a metalatom causes generation of an electron serving as a carrier. Thus, atransistor including an oxide semiconductor that contains hydrogen islikely to be normally-on. Accordingly, it is preferable that hydrogen inthe oxide semiconductor be reduced as much as possible. Specifically,the hydrogen concentration measured by SIMS is set lower than 1×10²⁰atoms/cm³, preferably lower than 1×10¹⁹ atoms/cm³, further preferablylower than 5×10¹⁸ atoms/cm³, and still further preferably lower than1×10¹⁸ atoms/cm³.

Note that oxygen vacancies (Vo) in the oxide semiconductor can bereduced by introduction of oxygen into the oxide semiconductor. That is,the oxygen vacancies (Vo) in the oxide semiconductor disappear when theoxygen vacancies (Vo) are filled with oxygen. Accordingly, diffusion ofoxygen in the oxide semiconductor can reduce the oxygen vacancies (Vo)in a transistor and improve the reliability of the transistor.

As a method for introducing oxygen into the oxide semiconductor, forexample, an oxide in which oxygen content is higher than that in thestoichiometric composition is provided in contact with the oxidesemiconductor. That is, in the oxide, a region including oxygen inexcess of that in the stoichiometric composition (hereinafter alsoreferred to as an excess-oxygen region) is preferably formed. Inparticular, in the case of using an oxide semiconductor in a transistor,an oxide including an excess-oxygen region is provided in a base film,an interlayer film, or the like in the vicinity of the transistor,whereby oxygen vacancies in the transistor are reduced, and thereliability can be improved.

When an oxide semiconductor with sufficiently reduced impurityconcentration is used for a channel formation region in a transistor,the transistor can have stable electrical characteristics.

<Method for Forming Oxide Semiconductor Material>

An example of a method for forming the oxide semiconductor material isdescribed below.

The oxide semiconductor is preferably deposited at a temperature higherthan or equal to room temperature and lower than 140° C. Note that roomtemperature includes not only the case where temperature control is notperformed but also the case where temperature control is performed,e.g., the case where a substrate is cooled.

As a sputtering gas, a rare gas (typically argon), oxygen, or a mixedgas of a rare gas and oxygen is used as appropriate. When the mixed gasis used, the proportion of the oxygen gas in the whole deposition gas ishigher than or equal to 5% and lower than or equal to 30%, preferablyhigher than or equal to 7% and lower than or equal to 20%.

When the sputtering gas contains oxygen, oxygen can be added to a filmunder the oxide semiconductor and an excess-oxygen region can beprovided at the same time as the deposition of the oxide semiconductor.In addition, increasing the purity of a sputtering gas is necessary. Forexample, when a gas which is highly purified to have a dew point of −40°C. or lower, preferably −80° C. or lower, further preferably −100° C. orlower, still further preferably −120° C. or lower, is used as asputtering gas, i.e., the oxygen gas or the argon gas, entry of moistureor the like into the oxide semiconductor can be minimized.

In the case where the oxide semiconductor is deposited by a sputteringmethod, a chamber in a sputtering apparatus is preferably evacuated tobe a high vacuum state (to the degree of about 5×10⁻⁷ Pa to 1×10⁻⁴ Pa)with an adsorption vacuum evacuation pump such as a cryopump in order toremove water or the like, which serves as an impurity for the oxidesemiconductor, as much as possible. Alternatively, a turbo molecularpump and a cold trap are preferably combined so as to prevent a backflowof a gas, especially a gas containing carbon or hydrogen from an exhaustsystem to the inside of the chamber.

As a target, an In—Ga—Zn metal oxide target can be used. For example, ametal oxide target where an atomic ratio [In]:[Ga]:[Zn] is 4:2:4.1,5:1:7, or a neighborhood thereof is preferably used.

In the sputtering apparatus, the target may be rotated or moved. Forexample, a magnet unit is oscillated vertically and/or horizontallyduring the deposition, whereby the composite oxide semiconductor of thepresent invention can be formed. For example, the target may be rotatedor moved with a beat (also referred to as rhythm, pulse, frequency,period, cycle, or the like) of greater than or equal to 0.1 Hz and lessthan or equal to 1 kHz. Alternatively, the magnet unit may be oscillatedwith a beat of greater than or equal to 0.1 Hz and less than or equal to1 kHz.

The oxide semiconductor of the present invention can be formed, forexample, in the following manner: a mixed gas of oxygen and a rare gasin which the proportion of oxygen is approximately 10% is used; thesubstrate temperature is 130° C.; and an In—Ga—Zn metal oxide targetwhere an atomic ratio [In]:[Ga]:[Zn] is 4:2:4.1 is oscillated during thedeposition.

The structure described in this embodiment can be used in appropriatecombination with any of the structures described in the otherembodiments or examples.

Embodiment 2

In this embodiment, semiconductor devices each including the oxidematerial of embodiments of the present invention, and manufacturingmethods thereof will be described with reference to FIGS. 3A to 3C,FIGS. 4A to 4C, FIGS. 5A and 5B, FIGS. 6A to 6D, FIGS. 7A to 7C, FIGS.8A to 8C, FIGS. 9A to 9C, FIGS. 10A to 10C, FIGS. 11A to 11C, and FIGS.12A to 12C.

Structure Example 1 of Transistor

FIG. 3A is a top view of a transistor 100 that is a semiconductor deviceincluding the oxide material of one embodiment of the present invention.FIG. 3B is a cross-sectional view taken along dashed-dotted line X1-X2in FIG. 3A. FIG. 3C is a cross-sectional view taken along dashed-dottedline Y1-Y2 in FIG. 3A. Note that in FIG. 3A, some components of thetransistor 100 (e.g., an insulating film functioning as a gateinsulating film) are not illustrated to avoid complexity. The directionof the dashed-dotted line X1-X2 may be called a channel lengthdirection, and the direction of the dashed-dotted line Y1-Y2 may becalled a channel width direction. As in FIG. 3A, some components are notillustrated in some cases in top views of transistors described below.

The transistor 100 illustrated in FIGS. 3A to 3C is what is called atop-gate transistor.

The transistor 100 includes an insulating film 104 over a substrate 102,an oxide semiconductor film 108 over the insulating film 104, aninsulating film 110 over the oxide semiconductor film 108, a conductivefilm 112 over the insulating film 110, and an insulating film 116 overthe insulating film 104, the oxide semiconductor film 108, and theconductive film 112.

In a region which overlaps with the conductive film 112, the oxidesemiconductor film 108 is provided over the insulating film 104. Forexample, the oxide semiconductor film 108 preferably contains In, M (Mis Al, Ga, Y, or Sn), and Zn.

The oxide semiconductor film 108 includes regions 108 n which do notoverlap with the conductive film 112 and are in contact with theinsulating film 116. The regions 108 n are n-type regions in the oxidesemiconductor film 108 described above. The regions 108 n are in contactwith the insulating film 116, and the insulating film 116 containsnitrogen or hydrogen. Nitrogen or hydrogen in the insulating film 116 isadded to the regions 108 n to increase the carrier density, therebymaking the regions 108 n n-type.

The oxide semiconductor film 108 preferably includes a region in whichthe atomic proportion of In is larger than the atomic proportion of M.For example, the atomic ratio of In to M and Zn in the oxidesemiconductor film 108 is preferably InM:Zn=4:2:3 or in the neighborhoodthereof.

Note that the composition of the oxide semiconductor film 108 is notlimited to the above. For example, the atomic ratio of In to M and Zn inthe oxide semiconductor film 108 is preferably In:M:Zn=5:1:6 or in theneighborhood thereof. The term “neighborhood” includes the following:when In is 5, M is greater than or equal to 0.5 and less than or equalto 1.5, and Zn is greater than or equal to 5 and less than or equal to7.

When the oxide semiconductor film 108 has a region in which the atomicproportion of In is larger than the atomic proportion of M, thetransistor 100 can have high field-effect mobility. Specifically, thefield-effect mobility of the transistor 100 can exceed 10 cm²/Vs,preferably exceed 30 cm²/Vs.

For example, the use of the transistor with high field-effect mobilityin a gate driver that generates a gate signal allows the display deviceto have a narrow frame. The use of the transistor with high field-effectmobility in a source driver (particularly in a demultiplexer connectedto an output terminal of a shift register included in a source driver)that is included in a display device and supplies a signal from a signalline can reduce the number of wirings connected to the display device.

Even when the oxide semiconductor film 108 includes a region in whichthe atomic proportion of In is higher than the atomic proportion of M,the field-effect mobility might be low if the oxide semiconductor film108 has high crystallinity.

Note that the crystallinity of the oxide semiconductor film 108 can bedetermined by analysis by X-ray diffraction (XRD) or with a transmissionelectron microscope (TEM), for example.

First, oxygen vacancies that might be formed in the oxide semiconductorfilm 108 will be described.

Oxygen vacancies formed in the oxide semiconductor film 108 adverselyaffect the transistor characteristics and therefore cause a problem. Forexample, hydrogen is trapped in oxygen vacancies formed in the oxidesemiconductor film 108 to serve as a carrier supply source. The carriersupply source generated in the oxide semiconductor film 108 causes achange in the electrical characteristics, typically, shift in thethreshold voltage, of the transistor 100 including the oxidesemiconductor film 108. Therefore, it is preferable that the amount ofoxygen vacancies in the oxide semiconductor film 108 be as small aspossible.

In one embodiment of the present invention, the insulating film in thevicinity of the oxide semiconductor film 108 contains excess oxygen.Specifically, one or both of the insulating film 110 which is formedover the oxide semiconductor film 108 and the insulating film 104 whichis formed below the oxide semiconductor film 108 contain excess oxygen.Oxygen or excess oxygen is transferred from the insulating film 104and/or the insulating film 110 to the oxide semiconductor film 108,whereby oxygen vacancies in the oxide semiconductor film can be reduced.

Impurities such as hydrogen and moisture entering the oxidesemiconductor film 108 adversely affect the transistor characteristicsand therefore cause a problem. Thus, it is preferable that the amount ofimpurities such as hydrogen and moisture in the oxide semiconductor film108 be as small as possible.

Note that it is preferable to use, as the oxide semiconductor film 108,an oxide semiconductor film in which the impurity concentration is lowand the density of defect states is low, in which case the transistorcan have more excellent electrical characteristics. Here, the state inwhich the impurity concentration is low and the density of defect statesis low (the amount of oxygen vacancies is small) is referred to as“highly purified intrinsic” or “substantially highly purifiedintrinsic”. A highly purified intrinsic or substantially highly purifiedintrinsic oxide semiconductor film has few carrier generation sources,and thus can have a low carrier density. Thus, a transistor in which achannel region is formed in the oxide semiconductor film rarely has anegative threshold voltage (is rarely normally on). A highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorfilm has a low density of defect states and accordingly has a lowdensity of trap states in some cases. Furthermore, the highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorfilm has an extremely low off-state current; even when an element has achannel width of 1×10⁶ μm and a channel length of 10 μm, the off-statecurrent can be less than or equal to the measurement limit of asemiconductor parameter analyzer, that is, less than or equal to 1×10⁻¹³A, at a voltage (drain voltage) between a source electrode and a drainelectrode of from 1 V to 10 V.

As illustrated in FIGS. 3A to 3C, the transistor 100 may further includean insulating film 118 over the insulating film 116, a conductive film120 a electrically connected to the region 108 n through an opening 141a formed in the insulating films 116 and 118; and a conductive film 120b electrically connected to the region 108 n through an opening 141 bformed in the insulating films 116 and 118.

Note that in this specification and the like, the insulating film 104may be referred to as a first insulating film, the insulating film 110may be referred to as a second insulating film, the insulating film 116may be referred to as a third insulating film, and the insulating film118 may be referred to as a fourth insulating film. The conductive films112, 120 a, and 120 b function as a gate electrode, a source electrode,and a drain electrode, respectively.

The insulating film 110 functions as a gate insulating film. Theinsulating film 110 includes an excess-oxygen region. Since theinsulating film 110 includes the excess-oxygen region, excess oxygen canbe supplied to the oxide semiconductor film 108. As a result, oxygenvacancies that might be formed in the oxide semiconductor film 108 canbe filled with excess oxygen, and the semiconductor device can have highreliability.

To supply excess oxygen to the oxide semiconductor film 108, excessoxygen may be supplied to the insulating film 104 that is formed belowthe oxide semiconductor film 108. In that case, excess oxygen containedin the insulating film 104 might also be supplied to the regions 108 n,which is not desirable because the resistance of the regions 108 n mightbe increased. In contrast, in the structure in which the insulating film110 formed over the oxide semiconductor film 108 contains excess oxygen,excess oxygen can be selectively supplied only to a region overlappingwith the conductive film 112.

<Components of Semiconductor Device>

Next, components of the semiconductor device in this embodiment will bedescribed in detail.

[Substrate]

There is no particular limitation on a material and the like of thesubstrate 102 as long as the material has heat resistance high enough towithstand at least heat treatment to be performed later. For example, aglass substrate, a ceramic substrate, a quartz substrate, a sapphiresubstrate, or the like may be used as the substrate 102. Alternatively,a single crystal semiconductor substrate or a polycrystallinesemiconductor substrate of silicon or silicon carbide, a compoundsemiconductor substrate of silicon germanium, an SOT substrate, or thelike can be used, or any of these substrates provided with asemiconductor element may be used as the substrate 102. In the casewhere a glass substrate is used as the substrate 102, a glass substratehaving any of the following sizes can be used: the 6th generation (1500mm×1850 mm), the 7th generation (1870 mm×2200 mm), the 8th generation(2200 mm×2400 mm), the 9th generation (2400 mm×2800 mm), and the 10thgeneration (2950 mm×3400 mm). Thus, a large-sized display device can befabricated.

Alternatively, a flexible substrate may be used as the substrate 102,and the transistor 100 may be provided directly on the flexiblesubstrate. Alternatively, a separation layer may be provided between thesubstrate 102 and the transistor 100. The separation layer can be usedwhen part or the whole of a semiconductor device formed over theseparation layer is separated from the substrate 102 and transferredonto another substrate. In such a case, the transistor 100 can betransferred to a substrate having low heat resistance or a flexiblesubstrate as well.

[First Insulating Film]

The insulating film 104 can be formed by a sputtering method, a CVDmethod, an evaporation method, a pulsed laser deposition (PLD) method, aprinting method, a coating method, or the like as appropriate. Forexample, the insulating film 104 can be formed to have a single-layerstructure or stacked-layer structure including an oxide insulating filmand/or a nitride insulating film. To improve the properties of theinterface with the oxide semiconductor film 108, at least a region ofthe insulating film 104 which is in contact with the oxide semiconductorfilm 108 is preferably formed using an oxide insulating film. When theinsulating film 104 is formed using an oxide insulating film from whichoxygen is released by heating, oxygen contained in the insulating film104 can be moved to the oxide semiconductor film 108 by heat treatment.

The thickness of the insulating film 104 can be greater than or equal to50 nm, greater than or equal to 100 nm and less than or equal to 3000nm, or greater than or equal to 200 nm and less than or equal to 1000nm. By increasing the thickness of the insulating film 104, the amountof oxygen released from the insulating film 104 can be increased. Inaddition, interface states at the interface between the insulating film104 and the oxide semiconductor film 108 and oxygen vacancies includedin the oxide semiconductor film 108 can be reduced.

For example, the insulating film 104 can be formed to have asingle-layer structure or stacked-layer structure including siliconoxide, silicon oxynitride, silicon nitride oxide, silicon nitride,aluminum oxide, hafnium oxide, gallium oxide, a Ga—Zn oxide, or thelike. In this embodiment, the insulating film 104 has a stacked-layerstructure including a silicon nitride film and a silicon oxynitridefilm. With the insulating film 104 having such a stack-layer structureincluding a silicon nitride film as a lower layer and a siliconoxynitride film as an upper layer, oxygen can be efficiently introducedinto the oxide semiconductor film 108.

[Conductive Film]

The conductive film 112 functioning as a gate electrode and theconductive films 120 a and 120 b functioning as a source electrode and adrain electrode can each be formed using a metal element selected fromchromium (Cr), copper (Cu), aluminum (Al), gold (Au), silver (Ag), zinc(Zn), molybdenum (Mo), tantalum (Ta), titanium (Ti), tungsten (W),manganese (Mn), nickel (Ni), iron (Fe), and cobalt (Co); an alloyincluding any of these metal elements as its component; an alloyincluding a combination of any of these metal elements; or the like.

Furthermore, the conductive films 112, 120 a, and 120 b can be formedusing an oxide conductor or an oxide semiconductor, such as an oxideincluding indium and tin (In—Sn oxide), an oxide including indium andtungsten (In—W oxide), an oxide including indium, tungsten, and zinc(In—W—Zn oxide), an oxide including indium and titanium (In—Ti oxide),an oxide including indium, titanium, and tin (In—Ti—Sn oxide), an oxideincluding indium and zinc (In—Zn oxide), an oxide including indium, tin,and silicon (In—Sn—Si oxide), or an oxide including indium, gallium, andzinc (In—Ga—Zn oxide).

Here, an oxide conductor is described. In this specification and thelike, an oxide conductor may be referred to as OC. For example, oxygenvacancies are formed in an oxide semiconductor, and then hydrogen isadded to the oxygen vacancies, so that a donor level is formed in thevicinity of the conduction band. This increases the conductivity of theoxide semiconductor; accordingly, the oxide semiconductor becomes aconductor. The oxide semiconductor having become a conductor can bereferred to as an oxide conductor. oxide semiconductors generallytransmit visible light because of their large energy gap. Since an oxideconductor is an oxide semiconductor having a donor level in the vicinityof the conduction band, the influence of absorption due to the donorlevel is small in an oxide conductor, and an oxide conductor has avisible light transmitting property comparable to that of an oxidesemiconductor.

It is particularly preferred to use the oxide conductor described abovefor the conductive film 112, in which case excess oxygen can be added tothe insulating film 110.

A Cu—X alloy film (X is Mn, Ni, Cr, Fe, Co, Mo, Ta, or Ti) may be usedas the conductive films 112, 120 a, and 120 b. The use of a Cu—X alloyfilm results in lower fabrication costs because the film can beprocessed by wet etching.

Among the above-mentioned metal elements, any one or more elementsselected from titanium, tungsten, tantalum, and molybdenum arepreferably included in the conductive films 112, 120 a, and 120 b. Atantalum nitride film is particularly preferable as each of theconductive films 112, 120 a, and 120 b. A tantalum nitride film hasconductivity and a high barrier property against copper or hydrogen.Because a tantalum nitride film releases little hydrogen from itself, itcan be favorably used as the conductive film in contact with the oxidesemiconductor film 108 or the conductive film in the vicinity of theoxide semiconductor film 108.

The conductive films 112, 120 a, and 120 b can be formed by electrolessplating. As a material that can be deposited by electroless plating, forexample, one or more elements selected from Cu, Ni, Al, Au, Sn, Co, Ag,and Pd can be used. It is further favorable to use Cu or Ag because theresistance of the conductive film can be reduced.

[Second Insulating Film]

As the insulating film 110 functioning as a gate insulating film of thetransistor 100, an insulating layer including at least one of thefollowing films formed by a plasma enhanced chemical vapor deposition(PECVD) method, a sputtering method, or the like can be used: a siliconoxide film, a silicon oxynitride film, a silicon nitride oxide film, asilicon nitride film, an aluminum oxide film, a hafnium oxide film, anyttrium oxide film, a zirconium oxide film, a gallium oxide film, atantalum oxide film, a magnesium oxide film, a lanthanum oxide film, acerium oxide film, and a neodymium oxide film. Note that the insulatingfilm 110 may have a two-layer structure or a stacked-layer structureincluding three or more layers.

The insulating film 110 that is in contact with the oxide semiconductorfilm 108 functioning as a channel region of the transistor 100 ispreferably an oxide insulating film and preferably includes a regionincluding oxygen in excess of the stoichiometric composition(excess-oxygen region). In other words, the insulating film 110 is aninsulating film capable of releasing oxygen. In order to provide theexcess-oxygen region in the insulating film 110, the insulating film 110is formed in an oxygen atmosphere, or the deposited insulating film 110is subjected to heat treatment in an oxygen atmosphere, for example.

In the case of using a stacked-layer structure containing hafnium oxidefor the insulating film 110, the following effects are attained. Hafniumoxide has higher dielectric constant than silicon oxide and siliconoxynitride. Therefore, by using hafnium oxide, the thickness of theinsulating film 110 can be made large as compared with the case of usingsilicon oxide; thus, leakage current due to tunnel current can be low.That is, it is possible to provide a transistor with a low off-statecurrent. Moreover, hafnium oxide having a crystal structure has a higherdielectric constant than hafnium oxide having an amorphous structure.Therefore, it is preferable to use hafnium oxide having a crystalstructure, in order to obtain a transistor with a low off-state current.Examples of the crystal structure include a monoclinic crystal structureand a cubic crystal structure. Note that one embodiment of the presentinvention is not limited to the above examples.

It is preferable that the insulating film 110 have few defects andtypically have as few signals observed by electron spin resonance (ESR)spectroscopy as possible. Examples of the signals include a signal dueto an E′ center observed at a g-factor of 2.001. Note that the E′ centeris due to the dangling bond of silicon. As the insulating film 110, asilicon oxide film or a silicon oxynitride film whose spin density of asignal due to the E′ center is lower than or equal to 3×10¹⁷ spins/cm³and preferably lower than or equal to 5×10¹⁶ spins/cm³ may be used.

In addition to the above-described signal, a signal due to nitrogendioxide (NO₂) might be observed in the insulating film 110. The signalis divided into three signals according to the N nuclear spin; a firstsignal, a second signal, and a third signal. The first signal isobserved at a g-factor of greater than or equal to 2.037 and less thanor equal to 2.039. The second signal is observed at a g-factor ofgreater than or equal to 2.001 and less than or equal to 2.003. Thethird signal is observed at a g-factor of greater than or equal to 1.964and less than or equal to 1.966.

It is suitable to use an insulating film whose spin density of a signaldue to nitrogen dioxide (NO₂) is higher than or equal to 1×10¹⁷spins/cm³ and lower than 1×10¹⁸ spins/cm³ as the insulating film 110,for example.

Note that a nitrogen oxide (NO)) such as nitrogen dioxide (NO₂) forms astate in the insulating film 110. The state is positioned in the energygap of the oxide semiconductor film 108. Thus, when nitrogen oxide (NO))is diffused to the interface between the insulating film 110 and theoxide semiconductor film 108, an electron might be trapped by the stateon the insulating film 110 side. As a result, the trapped electronremains in the vicinity of the interface between the insulating film 110and the oxide semiconductor film 108, leading to a positive shift of thethreshold voltage of the transistor. Accordingly, the use of a film witha low nitrogen oxide content as the insulating film 110 can reduce ashift of the threshold voltage of the transistor.

As an insulating film that releases a small amount of nitrogen oxide(NO_(x)), for example, a silicon oxynitride film can be used. Thesilicon oxynitride film releases more ammonia than nitrogen oxide(NO_(x)) in thermal desorption spectroscopy (TDS) analysis; the typicalreleased amount of ammonia is greater than or equal to 1×10¹⁸molecules/cm³ and less than or equal to 5×10¹⁹ molecules/cm³. Note thatthe released amount of ammonia is the total amount of ammonia releasedby heat treatment in a range of 50° C. to 650° C. or 50° C. to 550° C.in TDS analysis.

Since nitrogen oxide (NO_(x)) reacts with ammonia and oxygen in heattreatment, the use of an insulating film that releases a large amount ofammonia reduces nitrogen oxide (NO_(x)).

Note that in the case where the insulating film 110 is analyzed by SIMS,the nitrogen concentration in the film is preferably lower than or equalto 6×10²⁰ atoms/cm³.

[Oxide Semiconductor Film]

As the oxide semiconductor film 108, the material described above can beused.

<Atomic Ratio>

Preferred ranges of the atomic ratio of indium, the element M, and zinccontained in the oxide semiconductor according to the present inventionare described with reference to FIGS. 13A to 13C. Note that theproportion of oxygen atoms is not illustrated in FIGS. 13A to 13C. Theterms of the atomic ratio of indium, the element M, and zinc containedin the oxide semiconductor are denoted by [In], [M], and [Zn],respectively.

In FIGS. 13A to 13C, dashed lines indicate a line where the atomic ratio[In]:[M]:[Zn] is (1+α):(1−α):1 where α is a real number greater than orequal to −1 and less than or equal to 1, a line where the atomic ratio[In]:[M]:[Zn] is (1+α):(1−α):2, a line where the atomic ratio[In]:[M]:[Zn] is (1+α):(1−α):3, a line where the atomic ratio[In]:[M]:[Zn] is (1+α):(1−α):4, and a line where the atomic ratio[In]:[M]:[Zn] is (1+α):(1−α):5.

Dashed-dotted lines indicate a line where the atomic ratio [In][M]:[Zn]is 5:1:β where β is a real number greater than or equal to 0, a linewhere the atomic ratio [In]:[M]:[Zn] is 2:1:β, a line representing theatomic ratio [In]:[M]:[Zn] is 1:1:β, a line where the atomic ratio[In]:[M]:[Zn] is 1:2:β, a line where the atomic ratio [In]:[M]:[Zn] is1:3:β, and a line where the atomic ratio [In]:[M]:[Zn] is 1:4:β.

An oxide semiconductor where the atomic ratio [In]:[M]:[Zn] is 0:2:1 orin the neighborhood thereof in FIGS. 13A to 13C tends to have a spinelcrystal structure.

A plurality of phases (e.g., two phases or three phases) exist in theoxide semiconductor in some cases. For example, with an atomic ratio[In]:[M]:[Zn] that is close to 0:2:1, two phases of a spinel crystalstructure and a layered crystal structure are likely to exist. Inaddition, with an atomic ratio [In]:[M]:[Zn] that is close to 1:0:0, twophases of a bixbyite crystal structure and a layered crystal structureare likely to exist. In the case where a plurality of phases exist inthe oxide semiconductor, a grain boundary might be formed betweendifferent crystal structures.

A region A in FIG. 13A shows an example of the preferred ranges of theatomic ratio of indium to the element M and zinc contained in an oxidesemiconductor.

In addition, the oxide semiconductor containing indium in a higherproportion can have high carrier mobility (electron mobility). Thus, anoxide semiconductor having a high content of indium has higher carriermobility than an oxide semiconductor having a low content of indium.

In contrast, when the indium content and the zinc content in an oxidesemiconductor become lower, carrier mobility becomes lower. Thus, withan atomic ratio [In]:[M]:[Zn] that is and the neighborhood thereof(e.g., a region C in FIG. 13C), insulation performance becomes better.

Accordingly, the oxide semiconductor of one embodiment of the presentinvention preferably has an atomic ratio represented by the region A inFIG. 13A. With the atomic ratio, high carrier mobility is obtained.

An oxide semiconductor having an atomic ratio in the region A,particularly in a region B in FIG. 13B, has high carrier mobility andhigh reliability and is excellent.

Note that the region B includes an atomic ratio [In]:[M]:[Zn] that is4:2:3 to 4:2:4.1 and the vicinity thereof. The vicinity includes anatomic ratio [In]:[M]:[Zn] that is 5:3:4. Note that the region Bincludes an atomic ratio [In]:[M]:[Zn] that is 5:1:6 and the vicinitythereof and an atomic ratio [In]:[M]:[Zn] that is 5:1:7 and the vicinitythereof.

Note that the property of an oxide semiconductor is not uniquelydetermined by an atomic ratio. Even with the same atomic ratio, theproperty of an oxide semiconductor might be different depending on aformation condition. For example, in the case where the oxidesemiconductor is deposited with a sputtering apparatus, a film having anatomic ratio deviated from the atomic ratio of a target is formed. Inparticular, [Zn] in the film might be smaller than [Zn] in the targetdepending on the substrate temperature in deposition. Thus, theillustrated regions each represent an atomic ratio with which an oxidesemiconductor tends to have specific characteristics, and boundaries ofthe regions A to C are not clear.

In the case where the oxide semiconductor film 108 is formed of In-M-Znoxide, it is preferable to use a target including polycrystallineIn-M-Zn oxide as the sputtering target. Note that the atomic ratio ofmetal elements in the formed oxide semiconductor film 108 varies fromthe above atomic ratios of metal elements of the sputtering targets in arange of ±40%. For example, when a sputtering target used for the oxidesemiconductor film 108 has an atomic ratio In:Ga:Zn that is 4:2:4.1, theatomic ratio of the oxide semiconductor film 108 may be 4:2:3 or in theneighborhood thereof. When a sputtering target used for the oxidesemiconductor film 108 has an atomic ratio In:Ga:Zn that is 5:1:7, theatomic ratio of the oxide semiconductor film 108 may be 5:1:6 or in theneighborhood thereof.

The energy gap of the oxide semiconductor film 108 is 2 eV or more,preferably 2.5 eV or more. With the use of an oxide semiconductor havingsuch a wide energy gap, the off-state current of the transistor 100 canbe reduced.

Furthermore, the oxide semiconductor film 108 may have anon-single-crystal structure. Examples of the non-single-crystalstructure include a c-axis-aligned crystalline oxide semiconductor(CAAC-OS) which will be described later, a polycrystalline structure, amicrocrystalline structure, and an amorphous structure. Among thenon-single-crystal structures, an amorphous structure has the highestdensity of defect states.

[Third Insulating Film]

The insulating film 116 contains nitrogen or hydrogen. A nitrideinsulating film can be used as the insulating film 116, for example. Thenitride insulating film can be formed using silicon nitride, siliconnitride oxide, silicon oxynitride, or the like. The hydrogenconcentration in the insulating film 116 is preferably higher than orequal to 1×10²² atoms/cm³. The insulating film 116 is in contact withthe region 108 n of the oxide semiconductor film 108. Thus, theconcentration of an impurity (nitrogen or hydrogen) in the region 108 nin contact with the insulating film 116 is increased, leading to anincrease in the carrier density of the region 108 n.

[Fourth Insulating Film]

As the insulating film 118, an oxide insulating film can be used.Alternatively, a layered film of an oxide insulating film and a nitrideinsulating film can be used as the insulating film 118. The insulatingfilm 118 can be formed using, for example, silicon oxide, siliconoxynitride, silicon nitride oxide, aluminum oxide, hafnium oxide,gallium oxide, or Ga—Zn oxide.

Furthermore, the insulating film 118 preferably functions as a barrierfilm against hydrogen, water, and the like from the outside.

The thickness of the insulating film 118 can be greater than or equal to30 nm and less than or equal to 500 nm, or greater than or equal to 100nm and less than or equal to 400 nm.

Structure Example 2 of Transistor

Next, a structure of a transistor different from that in FIGS. 3A to 3Cwill be described with reference to FIGS. 4A to 4C.

FIG. 4A is a top view of the transistor 150. FIG. 4B is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 4A.FIG. 4C is a cross-sectional view taken along dashed-dotted line Y1-Y2in FIG. 4A.

The transistor 150 illustrated in FIGS. 4A to 4C includes the conductivefilm 106 over the substrate 102; the insulating film 104 over theconductive film 106; the oxide semiconductor film 108 over theinsulating film 104; the insulating film 110 over the oxidesemiconductor film 108; the conductive film 112 over the insulating film110; and the insulating film 116 over the insulating film 104, the oxidesemiconductor film 108, and the conductive film 112.

Note that the oxide semiconductor film 108 has a structure similar thatin the transistor 100 shown in FIGS. 3A to 3C. The transistor 150 shownin FIGS. 4A to 4C includes the conductive film 106 and an opening 143 inaddition to the components of the transistor 100 described above.

The opening 143 is provided in the insulating films 104 and 110. Theconductive film 106 is electrically connected to the conductive film 112through the opening 143. Thus, the same potential is applied to theconductive film 106 and the conductive film 112. Note that differentpotentials may be applied to the conductive film 106 and the conductivefilm 112 without providing the opening 143. Alternatively, theconductive film 106 may be used as a light-blocking film withoutproviding the opening 143. When the conductive film 106 is formed usinga light-blocking material, for example, light from the bottom thatirradiates a second region can be reduced.

In the case of the structure of the transistor 150, the conductive film106 functions as a first gate electrode (also referred to as abottom-gate electrode), the conductive film 112 functions as a secondgate electrode (also referred to as a top-gate electrode), theinsulating film 104 functions as a first gate insulating film, and theinsulating film 110 functions as a second gate insulating film.

The conductive film 106 can be formed using a material similar to theabove-described materials of the conductive films 112, 120 a, and 120 b.It is particularly suitable to use a material containing copper as theconductive film 106 because the resistance can be reduced. It isfavorable that, for example, each of the conductive films 106, 120 a,and 120 b has a stacked-layer structure in which a copper film is over atitanium nitride film, a tantalum nitride film, or a tungsten film. Inthat case, by using the transistor 150 as a pixel transistor and/or adriving transistor of a display device, parasitic capacitance generatedbetween the conductive films 106 and 120 a and between the conductivefilms 106 and 120 b can be reduced. Thus, the conductive films 106, 120a, and 120 b can be used not only as the first gate electrode, thesource electrode, and the drain electrode of the transistor 150, butalso as power supply wirings, signal supply wirings, connection wirings,or the like of the display device.

In this manner, unlike the transistor 100 described above, thetransistor 150 in FIGS. 4A to 4C has a structure in which a conductivefilm functioning as a gate electrode is provided over and under theoxide semiconductor film 108. As in the transistor 150, a semiconductordevice of one embodiment of the present invention may have a pluralityof gate electrodes.

As illustrated in FIGS. 4B and 4C, the oxide semiconductor film 108faces the conductive film 106 functioning as a first gate electrode andthe conductive film 112 functioning as a second gate electrode and ispositioned between the two conductive films functioning as the gateelectrodes.

Furthermore, the length of the conductive film 112 in the channel widthdirection is larger than the length of the oxide semiconductor film 108in the channel width direction. In the channel width direction, thewhole oxide semiconductor film 108 is covered with the conductive film112 with the insulating film 110 placed therebetween. Since theconductive film 112 is connected to the conductive film 106 through theopening 143 provided in the insulating films 104 and 110, a side surfaceof the oxide semiconductor film 108 in the channel width direction facesthe conductive film 112 with the insulating film 110 placedtherebetween.

In other words, the conductive film 106 and the conductive film 112 areconnected through the opening 143 provided in the insulating films 104and 110, and each include a region positioned outside an edge portion ofthe oxide semiconductor film 108.

Such a structure enables the oxide semiconductor film 108 included inthe transistor 150 to be electrically surrounded by electric fields ofthe conductive film 106 functioning as a first gate electrode and theconductive film 112 functioning as a second gate electrode. A devicestructure of a transistor, like that of the transistor 150, in whichelectric fields of the first gate electrode and the second gateelectrode electrically surround the oxide semiconductor film 108 inwhich a channel region is formed can be referred to as a surroundedchannel (S-channel) structure.

Since the transistor 150 has the S-channel structure, an electric fieldfor inducing a channel can be effectively applied to the oxidesemiconductor film 108 by the conductive film 106 or the conductive film112; thus, the current drive capability of the transistor 150 can beimproved and high on-state current characteristics can be obtained. As aresult of the high on-state current, it is possible to reduce the sizeof the transistor 150. Furthermore, since the transistor 150 has astructure in which the oxide semiconductor film 108 is surrounded by theconductive film 106 and the conductive film 112, the mechanical strengthof the transistor 150 can be increased.

When seen in the channel width direction of the transistor 150, anopening different from the opening 143 may be formed on the side of theoxide semiconductor film 108 on which the opening 143 is not formed.

When a transistor has a pair of gate electrodes between which asemiconductor film is positioned as in the transistor 150, one of thegate electrodes may be supplied with a signal A, and the other gateelectrode may be supplied with a fixed potential V_(b). Alternatively,one of the gate electrodes may be supplied with the signal A, and theother gate electrode may be supplied with a signal B. Alternatively, oneof the gate electrodes may be supplied with a fixed potential V_(a), andthe other gate electrode may be supplied with the fixed potential V_(b).

The signal A is, for example, a signal for controlling the on/off state.The signal A may be a digital signal with two kinds of potentials, apotential V1 and a potential V2 (V1>V2). For example, the potential V1can be a high power supply potential, and the potential V2 can be a lowpower supply potential. The signal A may be an analog signal.

The fixed potential V_(b) is, for example, a potential for controlling athreshold voltage V_(thA) of the transistor. The fixed potential V_(b)may be the potential V1 or the potential V2. In that case, a potentialgenerator circuit for generating the fixed potential V_(b) is notnecessary, which is preferable. The fixed potential V_(b) may bedifferent from the potential V1 or the potential V2. When the fixedpotential V_(b) is low, the threshold voltage V_(thA) can be high insome cases. As a result, the drain current flowing when the gate-sourcevoltage V_(gs) is 0 V can be reduced, and leakage current in a circuitincluding the transistor can be reduced in some cases. The fixedpotential V_(b) may be, for example, lower than the low power supplypotential. Meanwhile, a high fixed potential V_(b) can lower thethreshold voltage V_(thA) in some cases. As a result, the drain currentflowing when the gate-source voltage V_(gs) is a high power supplypotential and the operating speed of the circuit including thetransistor can be increased in some cases. The fixed potential V_(b) maybe, for example, higher than the low power supply potential.

The signal B is, for example, a signal for controlling the on/off state.The signal B may be a digital signal with two kinds of potentials, apotential V3 and a potential V4 (V3>V4). For example, the potential V3can be a high power supply potential, and the potential V4 can be a lowpower supply potential. The signal B may be an analog signal.

When both the signal A and the signal B are digital signals, the signalB may have the same digital value as the signal A. In this case, it maybe possible to increase the on-state current of the transistor and theoperating speed of the circuit including the transistor. Here, thepotential V1 and the potential V2 of the signal A may be different fromthe potential V3 and the potential V4 of the signal B. For example, if agate insulating film for the gate to which the signal B is input isthicker than a gate insulating film for the gate to which the signal Ais input, the potential amplitude of the signal B (V3−V4) may be largerthan the potential amplitude of the signal A (V1−V2). In this manner,the influence of the signal A and that of the signal B on the on/offstate of the transistor can be substantially the same in some cases.

When both the signal A and the signal B are digital signals, the signalB may have a digital value different from that of the signal A. In thiscase, the signal A and the signal B can separately control thetransistor, and thus, higher performance can be achieved. The transistorwhich is, for example, an n-channel transistor can function by itself asa NAND circuit, a NOR circuit, or the like in the following case: thetransistor is turned on only when the signal A has the potential V1 andthe signal B has the potential V3, or the transistor is turned off onlywhen the signal A has the potential V2 and the signal B has thepotential V4. The signal B may be a signal for controlling the thresholdvoltage V_(thA). For example, the potential of the signal B in a periodin which the circuit including the transistor operates may be differentfrom the potential of the signal B in a period in which the circuit doesnot operate. The potential of the signal B may vary depending on theoperation mode of the circuit. In this case, the potential of the signalB is not changed as frequently as the potential of the signal A in somecases.

When both the signal A and the signal B are analog signals, the signal Bmay be an analog signal having the same potential as the signal A, ananalog signal whose potential is a constant times the potential of thesignal A, an analog signal whose potential is higher or lower than thepotential of the signal A by a constant, or the like. In this case, itmay be possible to increase the on-state current of the transistor andthe operating speed of the circuit including the transistor. The signalB may be an analog signal different from the signal A. In this case, thesignal A and the signal B can separately control the transistor, andthus, higher performance can be achieved.

The signal A may be a digital signal, and the signal B may be an analogsignal. Alternatively, the signal A may be an analog signal, and thesignal B may be a digital signal.

When both of the gate electrodes of the transistor are supplied with thefixed potentials, the transistor can function as an element equivalentto a resistor in some cases. For example, in the case where thetransistor is an n-channel transistor, the effective resistance of thetransistor can be sometimes low (high) when the fixed potential V_(a) orthe fixed potential V_(b) is high (low). When both the fixed potentialV_(a) and the fixed potential V_(b) are high (low), the effectiveresistance can be lower (higher) than that of a transistor with only onegate in some cases. The other components of the transistor 150 aresimilar to those of the transistor 100 described above and have similareffects.

An insulating film may further be formed over the transistor 150. Thetransistor 150 illustrated in FIGS. 4A to 4C includes an insulating film122 over the conductive films 120 a and 120 b and the insulating film118.

The insulating film 122 has a function of covering unevenness and thelike caused by the transistor or the like. The insulating film 122 hasan insulating property and is formed using an inorganic material or anorganic material. Examples of the inorganic material include a siliconoxide film, a silicon oxynitride film, a silicon nitride oxide film, asilicon nitride film, an aluminum oxide film, and an aluminum nitridefilm. Examples of the organic material include photosensitive resinmaterials such as an acrylic resin and a polyimide resin.

Structure Example 3 of Transistor

Next, a structure of a transistor different from that of the transistor150 in FIGS. 4A to 4C will be described with reference to FIGS. 5A and5B.

FIGS. 5A and 5B are cross-sectional views of a transistor 160. The topview of the transistor 160 is not illustrated because it is similar tothat of the transistor 150 in FIG. 4A.

The transistor 160 illustrated in FIGS. 5A and 5B is different from thetransistor 150 in the stacked-layer structure of the conductive film112, the shape of the conductive film 112, and the shape of theinsulating film 110.

The conductive film 112 in the transistor 160 includes a conductive film112_1 over the insulating film 110 and a conductive film 112_2 over theconductive film 112_1. For example, an oxide conductive film is used asthe conductive film 112_1, so that excess oxygen can be added to theinsulating film 110. The oxide conductive film can be formed by asputtering method in an atmosphere containing an oxygen gas. As theoxide conductive film, an oxide including indium and tin, an oxideincluding tungsten and indium, an oxide including tungsten, indium, andzinc, an oxide including titanium and indium, an oxide includingtitanium, indium, and tin, an oxide including indium and zinc, an oxideincluding silicon, indium, and tin, an oxide including indium, gallium,and zinc, or the like can be used, for example.

As illustrated in FIG. 5B, the conductive film 1122 is connected to theconductive film 106 through the opening 143. By forming the opening 143after a conductive film to be the conductive film 112_1 is formed, theshape illustrated in FIG. 5B can be obtained. In the case where an oxideconductive film is used as the conductive film 112_1, the structure inwhich the conductive film 112_2 is connected to the conductive film 106can decrease the contact resistance between the conductive film 112 andthe conductive film 106.

The conductive film 112 and the insulating film 110 in the transistor160 have a tapered shape. More specifically, the lower edge portion ofthe conductive film 112 is positioned outside the upper edge portion ofthe conductive film 112. The lower edge portion of the insulating film110 is positioned outside the upper edge portion of the insulating film110. In addition, the lower edge portion of the conductive film 112 isformed in substantially the same position as that of the upper edgeportion of the insulating film 110.

As compared with the transistor 160 in which the conductive film 112 andthe insulating film 110 have a rectangular shape, the transistor 160 inwhich the conductive film 112 and the insulating film 110 have a taperedshape is favorable because of better coverage with the insulating film116.

The other components of the transistor 160 are similar to those of thetransistor 150 described above and have similar effects.

<Method for Manufacturing Semiconductor Device>

Next, a method for manufacturing the transistor 150 illustrated in FIGS.4A to 4C will be described with reference to FIGS. 6A to 6D, FIGS. 7A to7C, and FIGS. 8A to 8C. Note that FIGS. 6A to 6D, FIGS. 7A to 7C, andFIGS. 8A to 8C are cross-sectional views in the channel length directionand the channel width direction illustrating the method formanufacturing the transistor 150.

First, the conductive film 106 is formed over the substrate 102. Next,the insulating film 104 is formed over the substrate 102 and theconductive film 106, and an oxide semiconductor film is formed over theinsulating film 104. Then, the oxide semiconductor film is processedinto an island shape, whereby an oxide semiconductor film 108 a isformed (see FIG. 6A).

The conductive film 106 can be formed using a material selected from theabove-mentioned materials. In this embodiment, for the conductive film106, a stack including a 50-nm-thick tungsten film and a 400-nm-thickcopper film is formed with a sputtering apparatus.

To process a conductive film to be the conductive film 106, a wetetching method and/or a dry etching method can be used. In thisembodiment, in the processing of the conductive film into the conductivefilm 106, the copper film is etched by a wet etching method, and thenthe tungsten film is etched by a dry etching method.

The insulating film 104 can be formed by a sputtering method, a CVDmethod, an evaporation method, a pulsed laser deposition (PLD) method, aprinting method, a coating method, or the like as appropriate. In thisembodiment, as the insulating film 104, a 400-nm-thick silicon nitridefilm and a 50-nm-thick silicon oxynitride film are formed with a PECVDapparatus.

After the insulating film 104 is formed, oxygen may be added to theinsulating film 104. As oxygen added to the insulating film 104, anoxygen radical, an oxygen atom, an oxygen atomic ion, an oxygenmolecular ion, or the like may be used. Oxygen can be added by an iondoping method, an ion implantation method, a plasma treatment method, orthe like. Alternatively, a film that suppresses oxygen release may beformed over the insulating film 104, and then oxygen may be added to theinsulating film 104 through the film.

The film that suppresses oxygen release can be formed using a conductivefilm or a semiconductor film containing one or more of indium, zinc,gallium, tin, aluminum, chromium, tantalum, titanium, molybdenum,nickel, iron, cobalt, and tungsten.

In the case where oxygen is added by plasma treatment in which oxygen isexcited by a microwave to generate high-density oxygen plasma, theamount of oxygen added to the insulating film 104 can be increased.

In forming the oxide semiconductor film 108 a, an inert gas (such as ahelium gas, an argon gas, or a xenon gas) may be mixed into the oxygengas. Note that the proportion of the oxygen gas in the whole depositiongas (hereinafter also referred to as an oxygen flow rate ratio) informing the oxide semiconductor film 108 a is higher than or equal to 5%and lower than or equal to 30%, preferably higher than or equal to 7%and lower than or equal to 20%.

The oxide semiconductor film 108 a is formed at a substrate temperaturehigher than or equal to room temperature and lower than or equal to 180°C., preferably higher than or equal to room temperature and lower thanor equal to 140° C. The substrate temperature when the oxidesemiconductor film 108 a is formed is preferably, for example, higherthan or equal to room temperature and lower than 140° C. because theproductivity is increased.

The thickness of the oxide semiconductor film 108 a is greater than orequal to 3 nm and less than or equal to 200 nm, preferably greater thanor equal to 3 nm and less than or equal to 100 nm, further preferablygreater than or equal to 3 nm and less than or equal to 60 nm.

In the case where a large-sized glass substrate (e.g., the 6thgeneration to the 10th generation) is used as the substrate 102 and theoxide semiconductor film 108 a is formed at a substrate temperaturehigher than or equal to 200° C. and lower than or equal to 300° C., thesubstrate 102 might be changed in shape (distorted or warped).Therefore, in the case where a large-sized glass substrate is used, thechange in the shape of the glass substrate can be suppressed by formingthe oxide semiconductor film 108 a at a substrate temperature higherthan or equal to room temperature and lower than 200° C.

In addition, increasing the purity of the sputtering gas is necessary.For example, when a gas which is highly purified to have a dew point of−40° C. or lower, preferably −80° C. or lower, further preferably −100°C. or lower, still further preferably −120° C. or lower, is used as thesputtering gas, i.e., the oxygen gas or the argon gas, entry of moistureor the like into the oxide semiconductor film can be minimized.

In the case where the oxide semiconductor film is deposited by asputtering method, a chamber in a sputtering apparatus is preferablyevacuated to be a high vacuum state (to the degree of about 5×10⁻⁷ Pa to1×10⁻⁴ Pa) with an adsorption vacuum evacuation pump such as a cryopumpin order to remove water or the like, which serves as an impurity forthe oxide semiconductor film, as much as possible. In particular, thepartial pressure of gas molecules corresponding to H₂O (gas moleculescorresponding to m/z=18) in the chamber in the standby mode of thesputtering apparatus is preferably lower than or equal to 1×10⁻⁴ Pa,further preferably lower than or equal to 5×10⁻⁵ Pa.

In this embodiment, the oxide semiconductor film 108 a is formed in thefollowing conditions.

The oxide semiconductor film 108 a is formed by a sputtering methodusing an In—Ga—Zn metal oxide target. The substrate temperature and theoxygen flow rate at the time of formation of the oxide semiconductorfilm 108 a can be set as appropriate. An oxide material is formed underthe following conditions: the pressure in a chamber is 0.6 Pa; and an ACpower of 2500 W is supplied to the metal oxide target provided in thesputtering apparatus.

To process the formed oxide material into the oxide semiconductor film108 a, a wet etching method and/or a dry etching method can be used.

After the oxide semiconductor film 108 a is formed, the oxidesemiconductor film 108 a may be dehydrated or dehydrogenated by heattreatment. The temperature of the heat treatment is typically higherthan or equal to 150° C. and lower than the strain point of thesubstrate, higher than or equal to 250° C. and lower than or equal to450° C., or higher than or equal to 300° C. and lower than or equal to450° C.

The heat treatment can be performed in an inert gas atmospherecontaining nitrogen or a rare gas such as helium, neon, argon, xenon, orkrypton. Alternatively, the heat treatment may be performed in an inertgas atmosphere first, and then in an oxygen atmosphere. It is preferablethat the above inert gas atmosphere and the above oxygen atmosphere notcontain hydrogen, water, or the like. The treatment time may be longerthan or equal to 3 minutes and shorter than or equal to 24 hours.

An electric furnace, an RTA apparatus, or the like can be used for theheat treatment. With the use of an RTA apparatus, the heat treatment canbe performed at a temperature higher than or equal to the strain pointof the substrate if the heating time is short. Therefore, the heattreatment time can be shortened.

By depositing the oxide semiconductor film while it is heated or byperforming heat treatment after the deposition of the oxidesemiconductor film, the hydrogen concentration in the oxidesemiconductor film, which is measured by SIMS, can be 5×10¹⁹ atoms/cm³or lower, 1×10¹⁹ atoms/cm³ or lower, 5×10¹⁸ atoms/cm³ or lower, 1×10¹⁸atoms/cm³ or lower, 5×10¹⁷ atoms/cm³ or lower, or 1×10¹⁶ atoms/cm³ orlower.

Next, an insulating film 110_0 is formed over the insulating film 104and the oxide semiconductor film 108 a (see FIG. 6B).

For the insulating film 110_0, a silicon oxide film or a siliconoxynitride film can be formed with a plasma-enhanced chemical vapordeposition apparatus (also referred to as a PECVD apparatus or simply aplasma CVD apparatus). In this case, a deposition gas containing siliconand an oxidizing gas are preferably used as a source gas. Typicalexamples of the deposition gas containing silicon include silane,disilane, trisilane, and silane fluoride. Examples of the oxidizing gasinclude oxygen, ozone, dinitrogen monoxide, and nitrogen dioxide.

A silicon oxynitride film having few defects can be formed as theinsulating film 110_0 with the PECVD apparatus under the conditions thatthe flow rate of the oxidizing gas is more than 20 times and less than100 times, or more than or equal to 40 times and less than or equal totimes the flow rate of the deposition gas and that the pressure in atreatment chamber is lower than 100 Pa or lower than or equal to 50 Pa.

As the insulating film 110_0, a dense silicon oxide film or a densesilicon oxynitride film can be formed under the following conditions:the substrate placed in a vacuum-evacuated treatment chamber of thePECVD apparatus is held at a temperature higher than or equal to 280° C.and lower than or equal to 400° C.; the pressure in the treatmentchamber into which a source gas is introduced is set to be higher thanor equal to 20 Pa and lower than or equal to 250 Pa, preferably higherthan or equal to 100 Pa and lower than or equal to 250 Pa; and ahigh-frequency power is supplied to an electrode provided in thetreatment chamber.

The insulating film 110_0 may be formed by a PECVD method using amicrowave. A microwave refers to a wave in the frequency range of 300MHz to 300 GHz. In the case of using a microwave, electron temperatureand electron energy are low. Furthermore, in supplied power, theproportion of power used for acceleration of electrons is low, andtherefore, much more power can be used for dissociation and ionizationof molecules. Thus, plasma with a high density (high-density plasma) canbe excited. This method causes little plasma damage to the depositionsurface or a deposit, so that the insulating film 110_0 having fewdefects can be formed.

Alternatively, the insulating film 110_0 can also be formed by a CVDmethod using an organosilane gas. As the organosilane gas, any of thefollowing silicon-containing compound can be used: tetraethylorthosilicate (TEOS) (chemical formula: Si(OC₂H₅)₄); tetramethylsilane(TMS) (chemical formula: Si(CH₃)₄); tetramethylcyclotetrasiloxane(TMCTS); octamethylcyclotetrasiloxane (OMCTS); hexamethyldisilazane(HMDS); triethoxysilane (SiH(OC₂H₅)₃); trisdimethylaminosilane(SiH(N(CH₃)₂)₃); or the like. The insulating film 110_0 having highcoverage can be formed by a CVD method using an organosilane gas.

In this embodiment, as the insulating film 110_0, a 100-nm-thick siliconoxynitride film is formed with the PECVD apparatus.

Subsequently, a mask is formed by lithography in a desired position overthe insulating film 110_0, and then the insulating film 110_0 and theinsulating film 104 are partly etched, so that the opening 143 reachingthe conductive film 106 is formed (see FIG. 6C).

To form the opening 143, a wet etching method and/or a dry etchingmethod can be used. In this embodiment, the opening 143 is formed by adry etching method.

Next, a conductive film 112_0 is formed over the conductive film 106 andthe insulating film 110_0 so as to cover the opening 143. In the casewhere a metal oxide film is used as the conductive film 112_0, forexample, oxygen might be added to the insulating film 110_0 during theformation of the conductive film 112_0 (see FIG. 6D).

In FIG. 6D, oxygen added to the insulating film 110_0 is schematicallyshown by arrows. Furthermore, the conductive film 112_0 formed to coverthe opening 143 is electrically connected to the conductive film 106.

In the case where a metal oxide film is used as the conductive film1120, the conductive film 112_0 is preferably formed by a sputteringmethod in an atmosphere containing an oxygen gas. Formation of theconductive film 112_0 in an atmosphere containing an oxygen gas allowssuitable addition of oxygen to the insulating film 110_0. Note that amethod for forming the conductive film 112_0 is not limited to asputtering method, and another method such as an ALD method may be used.

In this embodiment, a 100-nm-thick IGZO film containing an In—Ga—Znoxide (In:Ga:Zn=4:2:4.1 (atomic ratio)) is formed as the conductive film112_0 by a sputtering method. Oxygen addition treatment may be performedon the insulating film 110_0 before or after the formation of theconductive film 112_0. The oxygen addition treatment can be performed ina manner similar to that of the oxygen addition treatment that can beperformed after the formation of the insulating film 104.

Subsequently, a mask 140 is formed by a lithography process in a desiredposition over the conductive film 112_0 (see FIG. 7A).

Next, etching is performed from above the mask 140 to process theconductive film 112_0 and the insulating film 110_0. After theprocessing of the conductive film 112_0 and the insulating film 110_0,the mask 140 is removed. As a result of the processing of the conductivefilm 112_0 and the insulating film 110_0, the island-shaped conductivefilm 112 and the island-shaped insulating film 110 are formed (see FIG.7B).

In this embodiment, the conductive film 112_0 and the insulating film110_0 are processed by a dry etching method.

In the processing of the conductive film 112_0 and the insulating film110_0, the thickness of the oxide semiconductor film 108 a in a regionnot overlapping with the conductive film 112 is decreased in some cases.In other cases, in the processing of the conductive film 112_0 and theinsulating film 110_0, the thickness of the insulating film 104 in aregion not overlapping with the oxide semiconductor film 108 a isdecreased. In the processing of the conductive film 112_0 and theinsulating film 110_0, an etchant or an etching gas (e.g., chlorine)might be added to the oxide semiconductor film 108 a or the constituentelement of the conductive film 112_0 or the insulating film 110_0 mightbe added to the oxide semiconductor film 108.

Next, the insulating film 116 is formed over the insulating film 104,the oxide semiconductor film 108, and the conductive film 112. By theformation of the insulating film 116, part of the oxide semiconductorfilm 108 a that is in contact with the insulating film 116 becomes theregions 108 n. Here, the oxide semiconductor film 108 a overlapping withthe conductive film 112 is the oxide semiconductor film 108 (see FIG.7C).

The insulating film 116 can be formed using a material selected from theabove-mentioned materials. In this embodiment, as the insulating film116, a 100-nm-thick silicon nitride oxide film is formed with a PECVDapparatus. In the formation of the silicon nitride oxide film, twosteps, i.e., plasma treatment and deposition treatment, are performed ata temperature of 220° C. The plasma treatment is performed under thefollowing conditions: an argon gas at a flow rate of 100 sccm and anitrogen gas at a flow rate of 1000 sccm are introduced into a chamberbefore deposition; the pressure in the chamber is set to 40 Pa; and apower of 1000 W is supplied to an RF power source (27.12 MHz). Thedeposition treatment is performed under the following conditions: asilane gas at a flow rate of 50 sccm, a nitrogen gas at a flow rate of5000 sccm, and an ammonia gas at a flow rate of 100 sccm are introducedinto the chamber; the pressure in the chamber is set to 100 Pa; and apower of 1000 W is supplied to the RF power source (27.12 MHz).

When a silicon nitride oxide film is used as the insulating film 116,nitrogen or hydrogen in the silicon nitride oxide film can be suppliedto the regions 108 n in contact with the insulating film 116. Inaddition, when the formation temperature of the insulating film 116 isthe above temperature, release of excess oxygen contained in theinsulating film 110 to the outside can be suppressed.

Next, the insulating film 118 is formed over the insulating film 116(see FIG. 8A).

The insulating film 118 can be formed using a material selected from theabove-mentioned materials. In this embodiment, as the insulating film118, a 300-nm-thick silicon oxynitride film is formed with a PECVDapparatus.

Subsequently, a mask is formed by lithography in a desired position overthe insulating film 118, and then the insulating film 118 and theinsulating film 116 are partly etched, so that the opening 141 a and theopening 141 b reaching the regions 108 n are formed (see FIG. 8B).

To etch the insulating film 118 and the insulating film 116, a wetetching method and/or a dry etching method can be used. In thisembodiment, the insulating film 118 and the insulating film 116 areprocessed by a dry etching method.

Next, a conductive film is formed over the regions 108 n and theinsulating film 118 so as to cover the openings 141 a and 141 b, and theconductive film is processed into a desired shape, whereby theconductive films 120 a and 120 b are formed (see FIG. 8C).

The conductive films 120 a and 120 b can be formed using a materialselected from the above-mentioned materials. In this embodiment, for theconductive films 120 a and 120 b, a stack including a 50-nm-thicktungsten film and a 400-nm-thick copper film is formed with a sputteringapparatus.

To process the conductive film to be the conductive films 120 a and 120b, a wet etching method and/or a dry etching method can be used. In thisembodiment, in the processing of the conductive film into the conductivefilms 120 a and 120 b, the copper film is etched by a wet etchingmethod, and then the tungsten film is etched by a dry etching method.

Then, the insulating film 122 is formed to cover the conductive films120 a and 120 b and the insulating film 118.

Through the above steps, the transistor 150 in FIGS. 4A to 4C can bemanufactured.

Note that the films included in the transistor 150 (the insulating film,the metal oxide film, the oxide semiconductor film, the conductive film,and the like) can be formed by, other than the above methods, asputtering method, a chemical vapor deposition (CVD) method, a vacuumevaporation method, a pulsed laser deposition (PLD) method, or an ALDmethod. Alternatively, a coating method or a printing method can beused. Although a sputtering method and a PECVD method are typicalexamples of the deposition method, a thermal CVD method may be used. Asan example of a thermal CVD method, a metal organic chemical vapordeposition (MOCVD) method can be given.

Deposition by the thermal CVD method may be performed in such a mannerthat the pressure in a chamber is set to an atmospheric pressure or areduced pressure, and a source gas and an oxidizer are supplied to thechamber at a time and react with each other in the vicinity of thesubstrate or over the substrate. Thus, no plasma is generated in thedeposition; therefore, the thermal CVD method has an advantage that nodefect due to plasma damage is caused.

The films such as the conductive films, the insulating films, the oxidesemiconductor films, and the metal oxide films that are described abovecan be formed by a thermal CVD method such as an MOCVD method.

For example, in the case where a hafnium oxide film is formed with adeposition apparatus employing an ALD method, two kinds of gases areused, namely, ozone (03) as an oxidizer and a source gas that isobtained by vaporizing liquid containing a solvent and a hafniumprecursor (hafnium alkoxide or hafnium amide such astetrakis(dimethylamide)hafnium (TDMAH, Hf[N(CH₃)₂]₄) ortetrakis(ethylmethylamide)hafnium).

In the case where an aluminum oxide film is formed with a depositionapparatus employing an ALD method, two kinds of gases are used, namely,H₂O as an oxidizer and a source gas that is obtained by vaporizingliquid containing a solvent and an aluminum precursor (e.g.,trimethylaluminum (TMA, Al(CH₃)₃)). Examples of another material includetris(dimethylamide)aluminum, triisobutylaluminum, and aluminumtris(2,2,6,6-tetramethyl-3,5-heptanedionate).

In the case where a silicon oxide film is formed with a depositionapparatus employing an ALD method, hexachlorodisilane is adsorbed on asurface on which a film is to be formed, and radicals of an oxidizinggas (O₂ or dinitrogen monoxide) are supplied to react with theadsorbate.

In the case where a tungsten film is formed with a deposition apparatusemploying an ALD method, a WF₆ gas and a B₂H₆ gas are sequentiallyintroduced to form an initial tungsten film, and then, a WF₆ gas and anH₂ gas are used to form a tungsten film. Note that an SiH₄ gas may beused instead of a B₂H₆ gas.

In the case where an oxide semiconductor film such as an In—Ga—Zn—O filmis formed with a deposition apparatus employing an ALD method, anIn(CH₃)₃ gas and an O₃ gas) are used to form an In—O layer, a Ga(CH₃)₃gas and an O₃ gas) are used to form a Ga—O layer, and then, a Zn(CH₃)₂gas and an O₃ gas) are used to form a Zn—O layer. Note that the order ofthese layers is not limited to this example. A mixed compound layer suchas an In—Ga—O layer, an In—Zn—O layer, or a Ga—Zn—O layer may be formedby using these gases. Note that although an H₂O gas that is obtained bybubbling water with an inert gas such as Ar may be used instead of an O₃gas), it is preferable to use an O₃ gas), which does not contain H.

Structure Example 4 of Transistor

FIG. 9A is a top view of a transistor 300A. FIG. 9B is a cross-sectionalview taken along dashed-dotted line X1-X2 in FIG. 9A. FIG. 9C is across-sectional view taken along dashed-dotted line Y1-Y2 in FIG. 9A.Note that in FIG. 9A, some components of the transistor 300A (e.g., aninsulating film functioning as a gate insulating film) are notillustrated to avoid complexity. The direction of the dashed-dotted lineX1-X2 may be referred to as a channel length direction, and thedirection of the dashed-dotted line Y1-Y2 may be referred to as achannel width direction. As in FIG. 9A, some components are notillustrated in some cases in top views of transistors described below.

The transistor 300A illustrated in FIGS. 9A to 9C includes a conductivefilm 304 over a substrate 302, an insulating film 306 over the substrate302 and the conductive film 304, an insulating film 307 over theinsulating film 306, an oxide semiconductor film 308 over the insulatingfilm 307, a conductive film 312 a over the oxide semiconductor film 308,and a conductive film 312 b over the oxide semiconductor film 308. Overthe transistor 300A, specifically, over the conductive films 312 a and312 b and the oxide semiconductor film 308, an insulating film 314, aninsulating film 316, and an insulating film 318 are provided.

In the transistor 300A, the insulating films 306 and 307 function as thegate insulating films of the transistor 300A, and the insulating films314, 316, and 318 function as protective insulating films of thetransistor 300A. Furthermore, in the transistor 300A, the conductivefilm 304 functions as a gate electrode, the conductive film 312 afunctions as a source electrode, and the conductive film 312 b functionsas a drain electrode.

In this specification and the like, the insulating films 306 and 307 maybe referred to as a first insulating film, the insulating films 314 and316 may be referred to as a second insulating film, and the insulatingfilm 318 may be referred to as a third insulating film.

The transistor 300A illustrated in FIGS. 9A to 9C is a channel-etchedtransistor. The oxide semiconductor film of one embodiment of thepresent invention is suitable for a channel-etched transistor.

Structure Example 5 of Transistor

FIG. 10A is a top view of a transistor 300B. FIG. 10B is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 10A.FIG. 10C is a cross-sectional view taken along dashed-dotted line Y1-Y2in FIG. 10A.

The transistor 300B illustrated in FIGS. 10A to 10C includes theconductive film 304 over the substrate 302, the insulating film 306 overthe substrate 302 and the conductive film 304, the insulating film 307over the insulating film 306, the oxide semiconductor film 308 over theinsulating film 307, the insulating film 314 over the oxidesemiconductor film 308, the insulating film 316 over the insulating film314, the conductive film 312 a electrically connected to the oxidesemiconductor film 308 through an opening 341 a provided in theinsulating films 314 and 316, and the conductive film 312 b electricallyconnected to the oxide semiconductor film 308 through an opening 341 bprovided in the insulating films 314 and 316. Over the transistor 300B,specifically, over the conductive films 312 a and 312 b and theinsulating film 316, the insulating film 318 is provided.

In the transistor 300B, the insulating films 306 and 307 each functionas a gate insulating film of the transistor 300B, the insulating films314 and 316 each function as a protective insulating film of the oxidesemiconductor film 308, and the insulating film 318 functions as aprotective insulating film of the transistor 300B. Moreover, in thetransistor 300B, the conductive film 304 functions as a gate electrode,the conductive film 312 a functions as a source electrode, and theconductive film 312 b functions as a drain electrode.

The transistor 300A illustrated in FIGS. 9A to 9C has a channel-etchedstructure, whereas the transistor 300B in FIGS. 10A to 10C has achannel-protective structure. The oxide semiconductor film of oneembodiment of the present invention is suitable for a channel-protectivetransistor as well.

Structure Example 6 of Transistor

FIG. 11A is a top view of a transistor 300C. FIG. 11B is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 11A.FIG. 11C is a cross-sectional view taken along dashed-dotted line Y1-Y2in FIG. 11A.

The transistor 300C illustrated in FIGS. 11A to 11C is different fromthe transistor 300B in FIGS. 10A to 10C in the shapes of the insulatingfilms 314 and 316. Specifically, the insulating films 314 and 316 of thetransistor 300C have island shapes and are provided over a channelregion of the oxide semiconductor film 308. Other components are similarto those of the transistor 300B.

Structure Example 7 of Transistor

FIG. 12A is a top view of a transistor 300D. FIG. 12B is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 12A.FIG. 12C is a cross-sectional view taken along dashed-dotted line Y1-Y2in FIG. 12A.

The transistor 300D illustrated in FIGS. 12A to 12C includes theconductive film 304 over the substrate 302, the insulating film 306 overthe substrate 302 and the conductive film 304, the insulating film 307over the insulating film 306, the oxide semiconductor film 308 over theinsulating film 307, the conductive film 312 a over the oxidesemiconductor film 308, the conductive film 312 b over the oxidesemiconductor film 308, the insulating film 314 over the oxidesemiconductor film 308 and the conductive films 312 a and 312 b, theinsulating film 316 over the insulating film 314, the insulating film318 over the insulating film 316, and conductive films 320 a and 320 bover the insulating film 318.

In the transistor 300D, the insulating films 306 and 307 function asfirst gate insulating films of the transistor 300D, and the insulatingfilms 314, 316, and 318 function as second gate insulating films of thetransistor 300D. Furthermore, in the transistor 300D, the conductivefilm 304 functions as a first gate electrode, the conductive film 320 afunctions as a second gate electrode, and the conductive film 320 bfunctions as a pixel electrode used for a display device. The conductivefilm 312 a functions as a source electrode, and the conductive film 312b functions as a drain electrode.

As illustrated in FIG. 12C, the conductive film 320 b is connected tothe conductive film 304 in an opening 342 b and an opening 342 cprovided in the insulating films 306, 307, 314, 316, and 318. Thus, thesame potential is applied to the conductive film 320 b and theconductive film 304.

The structure of the transistor 300D is not limited to that describedabove, in which the openings 342 b and 342 c are provided so that theconductive film 320 b is connected to the conductive film 304. Forexample, a structure in which only one of the openings 342 b and 342 cis provided so that the conductive film 320 b is connected to theconductive film 304, or a structure in which the conductive film 320 bis not connected to the conductive film 304 without providing theopenings 342 b and 342 c may be employed. Note that in the case wherethe conductive film 320 b is not connected to the conductive film 304,it is possible to apply different potentials to the conductive film 320b and the conductive film 304.

The conductive film 320 b is connected to the conductive film 312 bthrough an opening 342 a provided in the insulating films 314, 316, and318.

Note that the transistor 300D has the S-channel structure describedabove.

At least part of this embodiment can be implemented in combination withany of the other embodiments described in this specification asappropriate.

Example 1

In this example, measurement results of an oxide semiconductor of oneembodiment of the present invention over a substrate are described. Avariety of methods were used for the measurement. Note that in thisexample, Samples 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, and 1J were fabricated.

<<Structure of Samples and Fabrication Method Thereof>>

Samples 1A to 1H and 1J relating to one embodiment of the presentinvention are described below. Samples 1A to 1H and 1J each include asubstrate and an oxide semiconductor over the substrate.

Samples 1A to 1H and 1J were fabricated at different temperatures anddifferent oxygen flow rate ratios in formation of the oxidesemiconductor. The temperatures and the oxygen flow rate ratios information of the oxide semiconductors of Samples 1A to 1H and 1J areshown in Table 1 below.

TABLE 1 Flow rate Percentage Deposition [sccm] of O₂ temperature O₂ Ar[%] [° C.] Sample 1A 30 270 10 R.T. Sample 1B 90 210 30 R.T. Sample 1C300 0 100 R.T. Sample 1D 30 270 10 130 Sample 1E 90 210 30 130 Sample 1F300 0 100 130 Sample 1G 30 270 10 170 Sample 1H 90 210 30 170 Sample 1J300 0 100 170

Next, methods for fabricating the samples will be described.

A glass substrate was used as the substrate. Over the substrate, a100-nm-thick In—Ga—Zn oxide was formed as an oxide semiconductor with asputtering apparatus. The formation conditions were as follows: thepressure in a chamber was 0.6 Pa; and a metal oxide target (where anatomic ratio In:Ga:Zn is 4:2:4.1) was used as a target. The metal oxidetarget provided in the sputtering apparatus was supplied with an ACpower of 2500 W to form the oxide semiconductor.

The formation temperatures and oxygen flow rate ratios shown in theabove table were used as the conditions for forming oxide semiconductorsto fabricate Samples 1A to 1H and 1J.

Through the above steps, Samples 1A to 1H and 1J of this example werefabricated.

<Analysis by X-Ray Diffraction>

In this section, results of X-ray diffraction (XRD) measurementperformed on the oxide semiconductors over the glass substrates aredescribed. As an XRD apparatus, D8 ADVANCE manufactured by Bruker AXSwas used. The conditions were as follows: scanning was performed by anout-of-plane method at θ/2θ; the scanning range was 15 deg. to 50 deg.;the step width was 0.02 deg.; and the scanning speed was 3.0 deg./min.

FIG. 14 shows an XRD spectrum of the samples measured by an out-of-planemethod.

In the XRD spectra shown in FIG. 14 , the higher the substratetemperature at the time of formation is or the higher the oxygen gasflow rate ratio at the time of formation is, the higher the intensity ofthe peak at around 2θ=31° is. Note that it is found that the peak ataround 2θ=31° is derived from a crystalline IGZO compound whose c-axesare aligned in a direction substantially perpendicular to a formationsurface or a top surface of the crystalline IGZO compound (such acompound is also referred to as CAAC-IGZO).

As shown in the XRD spectra in FIG. 14 , as the substrate temperature atthe time of formation is lower or the oxygen gas flow rate ratio at thetime of formation is lower, a peak becomes less clear. Accordingly, itis found that there are no alignment in the a-b plane direction andc-axis alignment in the measured areas of the samples that are formed ata lower substrate temperature or with a lower oxygen gas flow rateratio.

<TEM Images and Electron Diffraction>

This section describes the observation and analysis results of Samples1A, 1D, and 1J with a high-angle annular dark-field scanningtransmission electron microscope (HAADF-STEM). An image obtained with anHAADF-STEM is also referred to as a TEM image.

This section describes electron diffraction patterns obtained byirradiation of Samples 1A, 1D, and 1J with an electron beam with a probediameter of 1 nm (also referred to as a nanobeam).

The plan-view TEM images were observed with a spherical aberrationcorrector function. The HAADF-STEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

Note that the electron diffraction patterns were observed while anelectron beam irradiation was performed at a constant rate for 35seconds.

FIG. 15A shows a cross-sectional TEM image of Sample 1A, and FIG. 15Bshows an electron diffraction pattern of Sample 1A. FIG. 15C shows across-sectional TEM image of Sample 1D, and FIG. 15D shows an electrondiffraction pattern of Sample 1D. FIG. 15E shows a cross-sectional TEMimage of Sample 1J, and FIG. 15F shows an electron diffraction patternof Sample 1J.

It is known that, for example, when an electron beam with a probediameter of 300 nm is incident on a CAAC-OS including an InGaZnO₄crystal in a direction parallel to the sample surface, a diffractionpattern including a spot derived from the (009) plane of the InGaZnO₄crystal is obtained. That is, the CAAC-OS has c-axis alignment and thec-axes are aligned in the direction substantially perpendicular to theformation surface or the top surface of the CAAC-OS. Meanwhile, aring-like diffraction pattern is shown when an electron beam with aprobe diameter of 300 nm is incident on the same sample in a directionperpendicular to the sample surface. That is, it is found that theCAAC-OS has neither a-axis alignment nor b-axis alignment.

Furthermore, a diffraction pattern like a halo pattern is observed whenan oxide semiconductor including a nanocrystal (a nanocrystalline oxidesemiconductor (hereinafter referred to as nc-OS)) is subjected toelectron diffraction using an electron beam with a large probe diameter(e.g., 50 nm or larger). Meanwhile, bright spots are shown in a nanobeamelectron diffraction pattern of the nc-OS obtained using an electronbeam with a small probe diameter (e.g., smaller than 50 nm).Furthermore, in a nanobeam electron diffraction pattern of the nc-OS,regions with high luminance in a circular (ring) pattern are shown insome cases. Also in a nanobeam electron diffraction pattern of thenc-OS, a plurality of bright spots are shown in a ring-like shape insome cases.

As shown in FIG. 15A, a nanocrystal (hereinafter, also referred to asnc) is observed in Sample 1A by cross-sectional TEM. In addition, asshown in FIG. 15B, the observed electron diffraction pattern of Sample1A has a region with high luminance in a circular (ring) pattern.Furthermore, a plurality of spots can be shown in the ring-shapedregion.

As shown in FIG. 15C, a CAAC structure and a nanocrystal are observed inSample 1D by cross-sectional TEM. In addition, as shown in FIG. 15D, theobserved electron diffraction pattern of Sample 1D has a region withhigh luminance in a circular (ring) pattern. Furthermore, a plurality ofspots can be shown in the ring-shaped region. In the diffractionpattern, spots derived from the (009) plane are slightly observed.

In contrast, as shown in FIG. 15E, layered arrangement of a CAACstructure is observed in Sample 1J by cross-sectional TEM.

The features observed in the cross-sectional TEM images and theplan-view TEM images are one aspect of a structure of an oxidesemiconductor.

Next, electron diffraction patterns obtained by irradiation of Sample 1Awith an electron beam with a probe diameter of 1 nm (also referred to asa nanobeam) are shown in FIGS. 16A to 16L.

Electron diffraction patterns of points indicated by black dots a1, a2,a3, a4, and a5 in the plan-view TEM image of Sample 1A in FIG. 16A areobserved. Note that the electron diffraction patterns are observed whileelectron beam irradiation is performed at a constant rate for 35seconds. FIGS. 16C, 16D, 16E, 16F, and 16G show the results of thepoints indicated by the black dots a1, a2, a3, a4, and a5, respectively.

In FIGS. 16C to 16G, regions with high luminance in a ring pattern wereshown. Furthermore, a plurality of spots are shown in the ring-shapedregions.

Electron diffraction patterns of points indicated by black dots b1, b2,b3, b4, and b5 in the cross-sectional TEM image of Sample 1A in FIG. 16Bare observed. FIGS. 16H, 16I, 16J, 16K, and 16L show the results of thepoints indicated by the black dots b1, b2, b3, b4, and b5, respectively.

In FIGS. 16H to 16L, regions with high luminance in a ring pattern areshown. Furthermore, a plurality of spots are shown in the ring-shapedregions.

In other words, it is found that Sample 1A has an nc structure and hascharacteristics distinctly different from those of an oxidesemiconductor film having an amorphous structure and an oxidesemiconductor film having a single crystal structure.

According to the above description, the electron diffraction patterns ofSample 1A and Sample 1D each have the region with high luminance in aring pattern and the plurality of bright spots appear in the ring-shapedregion. Thus, it is found that Sample 1A exhibits an electrondiffraction pattern of the nc-OS and does not show alignment in theplane direction and the cross-sectional direction. In addition, it isfound that Sample 1D has an nc structure and a CAAC structure.

In the electron diffraction pattern of Sample 1J, spots derived from the(009) plane of an InGaZnO₄ crystal are included. Thus, Sample 1J hasc-axis alignment and the c-axes are aligned in the directionsubstantially perpendicular to the formation surface or the top surfaceof Sample 1J.

<Analysis of TEM Image>

This section describes the observation and analysis results of Samples1A, 1C, 1D, 1F, 1G, and 1J with an HAADF-STEM.

The results of image analysis of plan-view TEM images are described. Theplan-view TEM images were obtained with a spherical aberration correctorfunction. The plan-view TEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

In FIG. 17 , the plan-view TEM images of Samples 1A, 1C, 1D, 1F, 1G, and1J and images obtained through image processing of the plan-view TEMimages are shown. Note that in a table in FIG. 17 , left views are theplan-view TEM images and right views are the images obtained throughimage processing of the plan-view TEM images on the left side.

Image processing and image analyzing methods are described. Imageprocessing was performed as follows. The plan-view TEM image in FIG. 17was subjected to fast Fourier transform (FFT), so that an FFT image wasobtained. Then, the obtained FFT image was subjected to mask processingexcept for a range from 2.8 nm⁻¹ to 5.0 nm⁻¹. After that, the FFT imagesubjected to mask processing was subjected to inverse fast Fouriertransform (IFFT) to obtain an FFT filtering image.

To conduct the image analysis, lattice points were extracted from theFFT filtering image in the following manner. First, noise in the FFTfiltering image was removed. To remove the noise, the luminance of aregion within a 0.05-nm radius was smoothed using Formula 1.

$\begin{matrix}\left\lbrack {{Formula}1} \right\rbrack &  \\{{{S\_ Int}\left( {x,y} \right)} = {\sum\limits_{r \leq 0.05}\frac{{Int}\left( {x^{\prime},y^{\prime}} \right)}{r}}} & (1)\end{matrix}$

Note that S_Int(x,y) represents the smoothed luminance at thecoordinates (x,y), r represents the distance between the coordinates(x,y) and the coordinates (x′,y′), and Int(x′,y′) represents theluminance at the coordinates (x′,y′). In the calculation, r is regardedas 1 when it is 0.

Then, a search for lattice points was conducted. The coordinates withthe highest luminance among candidate lattice points within a 0.22-nmradius were regarded as the lattice point. At this point, a candidatelattice point was extracted. Within a 0.22-nm radius, detection errorsof lattice points due to noise can be less frequent. Note that adjacentlattice points are a certain distance away from each other in the TEMimage; thus, two or more lattice points are unlikely to be observedwithin a 0.22-nm radius.

Subsequently, coordinates with the highest luminance within a 0.22-nmradius from the extracted candidate lattice point were extracted toredetermine a candidate lattice point. The extraction of a candidatelattice point was repeated in this manner until no new candidate latticepoint appeared; the coordinates at that point were determined as alattice point. Similarly, determination of another lattice point wasperformed at a position 0.22 nm or more away from the determined latticepoint; thus, lattice points were determined in the entire region. Thedetermined lattice points are collectively called a lattice point group.

Here, a method for deriving an orientation of a hexagonal lattice fromthe extracted lattice point group is described with reference toschematic diagrams in FIGS. 18A to 18C and a flow chart in FIG. 18D.First, a reference lattice point was determined and the six closestlattice points to the reference lattice point were connected to form ahexagonal lattice (see FIG. 18A and Step S101 in FIG. 18D). After that,an average distance R between the reference lattice point, which was thecenter point of the hexagonal lattice, and each of the lattice points,which is a vertex, was calculated. Then, a regular hexagon was formedwith the use of the reference lattice point as the center point and thecalculated distance R as the distance from the center point to eachvertex (see Step S102 in FIG. 18D). The distances from the vertices ofthe regular hexagon to their respective closest lattice points wereregarded as a distance d1, a distance d2, a distance d3, a distance d4,a distance d5, and a distance d6 (see FIG. 18B and Step S103 in FIG.18D). Next, the regular hexagon was rotated around the center pointthrough 60° by 0.1°, and the average deviation between the hexagonallattice and the rotated regular hexagon [D=(d1+d2+d3+d4+d5+d6)/6] wascalculated (see Step S104 in FIG. 18D). Then, a rotation angle θ of theregular hexagon when the average deviation D becomes minimum wascalculated as the orientation of the hexagonal lattice (see FIG. 18C andStep S105 in FIG. 18D). Next, an observation area of the plan-view TEMimage was adjusted so that hexagonal lattices whose orientations were30° account for the highest percentage. In such a condition, the averageorientation of hexagonal lattice within a 1-nm radius was calculated.The plan-view TEM image obtained through image processing was shownwhere color or gradation changes in accordance with the angle of thehexagonal lattice in the region. The image obtained through imageprocessing of the plan-view TEM image in FIG. 17 is an image obtained byperforming image analysis on the plan-view TEM image in FIG. 17 by theabove method and applying color in accordance with the angle of thehexagonal lattice. In other words, the image obtained through the imageprocessing of the plan-view TEM image is an image in which theorientations of lattice points in certain wavenumber ranges areextracted by color-coding the certain wavenumber ranges in an FFTfiltering image of the plan-view TEM image.

As shown in FIG. 17 , in Samples 1A and 1D in which nc is observed, thehexagons are oriented randomly and distributed in a mosaic pattern. InSample 1J in which a layered structure is observed in thecross-sectional TEM image, regions with uniformly oriented hexagonsexist in a large area of several tens of nanometers. In Sample 1D, it isfound that an nc region in a random mosaic pattern and a large-arearegion with uniformly oriented hexagons as in Sample 1J are included.

It is found from FIG. 17 that as the substrate temperature at the timeof formation is lower or the oxygen gas flow rate ratio at the time offormation is lower, regions in which the hexagons are oriented randomlyand distributed in a mosaic pattern are likely to exist.

Through the analysis of a plan-view TEM image of a CAAC-OS, a boundaryportion where angles of hexagonal lattices change can be examined.

Next, Voronoi diagrams were formed using lattice point groups in Sample1A. A Voronoi diagram is an image partitioned by regions including alattice point group. Each lattice point is closer to regions surroundingthe lattice point than to any other lattice point. A method for forminga Voronoi diagram is described below in detail using schematic diagramsin FIGS. 19A to 19D and a flow chart in FIG. 19E.

First, a lattice point group was extracted by the method described usingFIGS. 18A to 18D or the like (see FIG. 19A and Step S111 in FIG. 19E).Next, adjacent lattice points were connected with segments (see FIG. 19Band Step S112 in FIG. 19E). Then, perpendicular bisectors of thesegments were drawn (see FIG. 19C and Step S113 in FIG. 19E).Subsequently, points where three perpendicular bisectors intersect wereextracted (see Step S114 in FIG. 19E). The points are called Voronoipoints. After that, adjacent Voronoi points were connected with segments(see FIG. 19D and Step S115 in FIG. 19E). A polygonal region surroundedby the segments at this point is called a Voronoi region. In the abovemethod, a Voronoi diagram was formed.

FIG. 20 shows the proportions of the shapes of Voronoi regions(tetragon, pentagon, hexagon, heptagon, octagon, and enneagon) inSamples 1A, 1C, 1D, 1F, 1G, and 1J. Bar graphs show the numbers of theshapes of Voronoi regions (tetragon, pentagon, hexagon, heptagon,octagon, and enneagon) in the samples. Furthermore, tables show theproportions of the shapes of Voronoi regions (tetragon, pentagon,hexagon, heptagon, octagon, and enneagon) in the samples.

It is found from FIG. 20 that there is a tendency that the proportion ofhexagons is high in Sample 1J with a high degree of crystallinity andthe proportion of hexagons is low in Sample 1A with a low degree ofcrystallinity. The proportion of hexagons in Sample 1D is between thosein Samples 1J and 1A. Accordingly, it is found from FIG. 20 that thecrystal state of the oxide semiconductor significantly differs underdifferent formation conditions.

It is found from FIG. 20 that as the substrate temperature at the timeof formation is lower or the oxygen gas flow rate ratio at the time offormation is lower, the degree of crystallinity is lower and theproportion of hexagons is lower.

<Elementary Analysis>

This section describes the analysis results of elements included inSample 1A. For the analysis, by energy dispersive X-ray spectroscopy(EDX), EDX mapping images are obtained. An energy dispersive X-rayspectrometer AnalysisStation JED-2300T manufactured by JEOL Ltd. is usedas an elementary analysis apparatus in the EDX measurement. A Si driftdetector is used to detect an X-ray emitted from the sample.

In the EDX measurement, an EDX spectrum of a point is obtained in such amanner that electron beam irradiation is performed on the point in adetection target region of a sample, and the energy of characteristicX-ray of the sample generated by the irradiation and its frequency aremeasured. In this example, peaks of an EDX spectrum of the point wereattributed to electron transition to the L shell in an In atom, electrontransition to the K shell in a Ga atom, and electron transition to the Kshell in a Zn atom and the K shell in an O atom, and the proportions ofthe atoms in the point are calculated. An EDX mapping image indicatingdistributions of proportions of atoms can be obtained through theprocess in an analysis target region of a sample.

FIGS. 21A to 21H show a cross-sectional TEM image, a plan-view TEMimage, and EDX mapping images of Sample 1A. In the EDX mapping images,the proportion of an element is indicated by grayscale: the moremeasured atoms exist in a region, the brighter the region is; the lessmeasured atoms exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIGS. 21B to 21D and 21F to21H is 7,200,000 times.

FIG. 21A shows a cross-sectional TEM image, and FIG. 21E shows aplan-view TEM image. FIG. 21B shows a cross-sectional EDX mapping imageof In atoms, and FIG. 21F shows a plan-view EDX mapping image of Inatoms. In the EDX mapping image in FIG. 21B, the proportion of the Inatoms in all the atoms is 9.28 atomic % to 33.74 atomic %. In the EDXmapping image in FIG. 21F, the proportion of the In atoms in all theatoms is 12.97 atomic % to 38.01 atomic %.

FIG. 21C shows a cross-sectional EDX mapping image of Ga atoms, and FIG.21G shows a plan-view EDX mapping image of Ga atoms. In the EDX mappingimage in FIG. 21C, the proportion of the Ga atoms in all the atoms is1.18 atomic % to 18.64 atomic %. In the EDX mapping image in FIG. 21G,the proportion of the Ga atoms in all the atoms is 1.72 atomic % to19.82 atomic %.

FIG. 21D shows a cross-sectional EDX mapping image of Zn atoms, and FIG.21H shows a plan-view EDX mapping image of Zn atoms. In the EDX mappingimage in FIG. 21D, the proportion of the Zn atoms in all the atoms is6.69 atomic % to 24.99 atomic %. In the EDX mapping image in FIG. 21H,the proportion of the Zn atoms in all the atoms is 9.29 atomic % to28.32 atomic %.

Note that FIGS. 21A to 21D show the same region in the cross section ofSample 1A. FIGS. 21E to 21H show the same region in the plane of Sample1A.

FIGS. 22A to 22C show enlarged cross-sectional EDX mapping images ofSample 1A. FIG. 22A is an enlarged view of a part in FIG. 21B. FIG. 22Bis an enlarged view of a part in FIG. 21C. FIG. 22C is an enlarged viewof a part in FIG. 21D.

The EDX mapping images in FIGS. 22A to 22C show relative distribution ofbright and dark areas, indicating that the atoms have distributions inSample 1A. Areas surrounded by solid lines and areas surrounded bydashed lines in FIGS. 22A to 22C are examined.

As shown in FIG. 22A, a relatively dark region occupies a large area inthe area surrounded by the solid line and a relatively bright regionoccupies in a large area in the area surrounded by the dashed line. Asshown in FIG. 22B, a relatively bright region occupies a large area inthe area surrounded by the solid line and a relatively dark regionoccupies a large area in the area surrounded by the dashed line.

That is, it is found that the areas surrounded by the solid lines areregions including a relatively large number of In atoms and the areassurrounded by the dashed lines are regions including a relatively smallnumber of In atoms. FIG. 22C shows that a right portion of the areasurrounded by the solid line is relatively bright and a left portionthereof is relatively dark. Thus, it is found that the area surroundedby the solid line is a region including In_(X2)Zn_(Y2)O_(Z2), InO_(X1),or the like as a main component.

It is found that the area surrounded by the solid line is a regionincluding a relatively small number of Ga atoms and the area surroundedby the dashed line is a region including a relatively large number of Gaatoms. FIG. 22C shows that an upper left portion of the area surroundedby the dashed line is relatively dark and a lower right portion thereofis relatively bright. Thus, it is found that the area surrounded by thedashed line is a region including GaO_(X3), Ga_(X4)Zn_(Y4)O_(Z4), or thelike as a main component.

Furthermore, as shown in FIGS. 22A to 22C, the In atoms are relativelymore uniformly distributed than the Ga atoms, and regions includingInO_(X1) as a main component are seemingly joined to each other througha region including In_(X2)Zn_(Y2)O_(Z2) as a main component. It can bethus guessed that the regions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)as a main component extend like a cloud.

An In—Ga—Zn oxide having a composition in which the regions includingGaO_(X3) as a main component and the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component are unevenlydistributed and mixed can be referred to as CAC-IGZO.

As shown in FIGS. 22A to 22C, each of the regions including GaO_(X3) asa main component and the regions including In_(X2)Zn_(Y2)O_(Z2) orInO_(X1) as a main component has a size of greater than or equal to 0.5nm and less than or equal to 10 nm, or greater than or equal to 1 nm andless than or equal to 3 nm.

As described above, it is confirmed that the CAC-IGZO has a structuredifferent from that of an IGZO compound in which metal elements areevenly distributed, and has characteristics different from those of theIGZO compound. That is, it can be confirmed that in the CAC-IGZO,regions including GaO_(X3) or the like as a main component and regionsincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component areseparated to form a mosaic pattern.

Accordingly, it can be expected that when CAC-IGZO is used for asemiconductor element, the property derived from GaO_(X3) or the likeand the property derived from In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)complement each other, whereby high on-state current (Ion), highfield-effect mobility (μ) and low off-state current (I_(off)) can beachieved. A semiconductor element including CAC-IGZO has highreliability. Thus, CAC-IGZO is suitably used in a variety ofsemiconductor devices typified by a display.

At least part of this example can be implemented in combination with anyof embodiments and the other examples described in this specification asappropriate.

Example 2

In this example, the transistor 150 including the oxide semiconductorfilm 108 of one embodiment of the present invention was fabricated andsubjected to tests for electrical characteristics and reliability. Inthis example, nine transistors, i.e., Samples 2A, 2B, 2C, 2D, 2E, 2F,2G, 2H, and 2J, were fabricated as the transistor 150 including theoxide semiconductor 108.

<Structure of Samples and Fabrication Method Thereof>

Samples 2A to 2H and 2J relating to one embodiment of the presentinvention are described below. As Samples 2A to 2H and 2J, thetransistors 150 having the structure illustrated in FIGS. 3A to 3C werefabricated by the fabrication method described in Embodiment 2 withreference to FIGS. 6A to 6D, FIGS. 7A to 7C, and FIGS. 8A to 8C.

Samples 2A to 2H and 2J were fabricated at different temperatures anddifferent oxygen flow rate ratios in formation of the oxidesemiconductor 108. The temperatures and the oxygen flow rate ratios information of the oxide semiconductors of Samples 2A to 2H and 2J areshown in Table 2 below.

TABLE 2 Formation conditions of oxide semiconductor film 108 Flow ratePercentage Deposition [sccm] of O₂ temperature O₂ Ar [%] [° C.] Sample2A 30 270 10 R.T. Sample 2B 90 210 30 R.T. Sample 2C 300 0 100 R.T.Sample 2D 30 270 10 130 Sample 2E 90 210 30 130 Sample 2F 300 0 100 130Sample 2G 30 270 10 170 Sample 2H 90 210 30 170 Sample 2J 300 0 100 170

The samples were fabricated by the fabrication method described inEmbodiment 2. The oxide semiconductor 108 was formed using a metal oxidetarget (In:Ga:Zn=4:2:4.1 [atomic ratio]).

The transistor 150 had a channel length of 2 μm and a channel width of 3μm (hereinafter, also referred to as L/W=2/3 μm) or a channel length of2 μm and a channel width of 50 μm (hereinafter, also referred to asL/W=2/50 μm).

<I_(d)-V_(g) Characteristics of Transistors>

Next, I_(d)-V_(g) characteristics of the transistors (L/W=2/3 μm) inSamples 2A to 2H and 2J were measured. As conditions for measuring theI_(d)-V_(g) characteristics of each transistor, a voltage applied to theconductive film 112 serving as a first gate electrode (hereinafter thevoltage is also referred to as gate voltage (V g)) and a voltage appliedto the conductive film 106 serving as a second gate electrode(hereinafter the voltage is also referred to as back gate voltage (V_(b)g)) were changed from −10 V to +10 V in increments of 0.25 V. A voltageapplied to the conductive film 120 a serving as a source electrode (thevoltage is also referred to as source voltage (Vs)) was 0 V (comm), anda voltage applied to the conductive film 120 b serving as a drainelectrode (the voltage is also referred to as drain voltage (V_(d))) was0.1 V and 20 V.

In FIG. 23 , the results of I_(d)-V_(g) characteristics and field-effectmobilities of Samples 2A to 2H and 2J are shown. The solid line and thedashed-dotted line represent I_(d) at V_(d)=20 V and I_(d) at V_(d)=0.1V, respectively. The dashed line represents field-effect mobility. InFIG. 23 , the first vertical axis represents I_(d) [A], the secondvertical axis represents field-effect mobility (μFE) [cm²/Vs], and thehorizontal axis represents V_(g) [V]. The field-effect mobility wascalculated from the value measured at V_(d)=20 V.

As shown in FIG. 23 , it is found that Samples 2A to 2H and 2J havedifferent on-state currents (Ion) and different field effect mobilities,particularly different field effect mobilities in saturation regions. Inparticular, the maximum saturation mobilities and the risingcharacteristics of the field-effect mobilities around 0 V differdistinctly.

It is found from FIG. 23 that as the substrate temperature at the timeof formation is lower or the oxygen flow rate ratio at the time offormation is lower, the on-state current (Ion) becomes higher and thefield effect mobility rises more steeply around 0 V. In particular,Sample 2A has a maximum field-effect mobility close to 70 cm²/Vs.

<Gate Bias-Temperature Stress Test (GBT Test)>

Next, the reliability of the transistors (L/W=2/50 μm) of Samples 2A to2H and 2J was evaluated. As the reliability evaluation, GBT tests wereused.

The conditions for GBT tests in this example were as follows. A voltageapplied to the conductive film 112 serving as the first gate electrodeand the conductive film 106 serving as the second gate electrode(hereinafter referred to as gate voltage (V g)) was ±30 V, and a voltageapplied to the conductive film 120 a serving as the source electrode andthe conductive film 120 b serving as a drain electrode (hereinafterreferred to as source voltage (Vs) and drain voltage (V_(d)),respectively) was 0 V (COMMON). The stress temperature was 60° C., thetime for stress application was 1 hour, and two kinds of measurementenvironments, a dark environment and a photo environment (irradiationwith light at approximately 10,000 lx from a white LED), were employed.

In other words, the conductive film 120 a serving as the sourceelectrode of the transistor 150 and the conductive film 120 b serving asthe drain electrode of the transistor 150 were set at the samepotential, and a potential different from that of the conductive film120 a serving as the source electrode and the conductive film 120 bserving as the drain electrode was applied to the conductive film 112serving as the first gate electrode and the conductive film 106 servingas the second gate electrode for a certain time (here, one hour).

A case where the potential applied to the conductive film 112 serving asthe first gate electrode and the conductive film 106 serving as thesecond gate electrode is higher than the potential applied to theconductive film 120 a serving as the source electrode and the conductivefilm 120 b serving as the drain electrode is called positive stress, anda case where the potential applied to the conductive film 112 serving asthe first gate electrode and the conductive film 106 serving as thesecond gate electrode is lower than the potential applied to theconductive film 120 a serving as the source electrode and the conductivefilm 120 b serving as the drain electrode is called negative stress.Thus, the reliability evaluation was performed under four conditions intotal, i.e., positive GBT (dark), negative GBT (dark), positive GBT(light irradiation), and negative GBT (light irradiation).

Note that the positive GBT (dark) can be referred to as positive biastemperature stress (PBTS), the negative GBT (dark) as negative biastemperature stress (NBTS), the positive GBT (light irradiation) aspositive bias illumination temperature stress (PBITS), and the negativeGBT (light irradiation) as negative bias illumination temperature stress(NBITS).

FIG. 24 shows the GBT test results of Samples 2A to 2H and 2J. In FIG.24 , the vertical axis represents the amount of shift in the thresholdvoltage (ΔV_(th)) of the transistors.

The results in FIG. 24 indicate that the amount of shift in thethreshold voltage (ΔV_(th)) of each of the transistors included inSamples 2A to 2H and 2J was within ±3 V in the GBT tests. Thus, it isconfirmed that the transistors included in Samples 2A to 2H and 2J eachhave high reliability.

Thus, even the IGZO film having low crystallinity is presumed to have alow density of defect states like an IGZO film having highcrystallinity.

At least part of this example can be implemented in combination with anyof embodiments and the other examples described in this specification asappropriate.

Example 3

In this example, measurement results of an oxide semiconductor of oneembodiment of the present invention formed over a substrate aredescribed. A variety of methods were used for the measurement. Note thatin this example, Samples 3A, 3D, and 3J were fabricated.

<<Structure of Samples and Fabrication Method Thereof>>

Samples 3A, 3D, and 3J relating to one embodiment of the presentinvention are described below. Samples 3A, 3D, and 3J each include asubstrate and an oxide semiconductor over the substrate.

Samples 3A, 3D, and 3J were fabricated at different temperatures anddifferent oxygen flow rate ratios in formation of the oxidesemiconductor. The temperatures and the oxygen flow rate ratios information of the oxide semiconductors of Samples 3A, 3D, and 3J areshown in Table 3 below.

TABLE 3 Flow rate Percentage Deposition [sccm] of O₂ temperature O₂ Ar[%] [° C.] Sample 3A  30 270 10 R.T. Sample 3D  30 270 10 130 Sample 3J150 150 50 170

Next, methods for fabricating the samples will be described.

A glass substrate was used as the substrate. Over the substrate, a100-nm-thick In—Ga—Zn oxide semiconductor was formed as an oxidesemiconductor with a sputtering apparatus. The formation conditions wereas follows: the pressure in a chamber was 0.6 Pa, and a metal oxidetarget (where an atomic ratio In:Ga:Zn is 1:1:1.2) was used as a target.The metal oxide target provided in the sputtering apparatus was suppliedwith an AC power of 2500 W.

The formation temperatures and oxygen flow rate ratios shown in theabove table were used as the conditions for forming oxide semiconductorsto fabricate Samples 3A, 3D, and 3J.

Through the above steps, Samples 3A, 3D, and 3J of this example werefabricated.

<TEM Images and Electron Diffraction>

This section describes the TEM observation and analysis results ofSamples 3A, 3D, and 3J.

This section describes electron diffraction patterns obtained byirradiation of Samples 3A, 3D, and 3J with an electron beam with a probediameter of 1 nm (also referred to as a nanobeam).

The plan-view TEM images were observed with a spherical aberrationcorrector function. The HAADF-STEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV, and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

Note that the electron diffraction patterns were observed while anelectron beam irradiation was performed at a constant rate for 35seconds.

FIG. 25A shows a cross-sectional TEM image of Sample 3A, and FIG. 25Bshows an electron diffraction pattern of Sample 3A. FIG. 25C shows across-sectional TEM image of Sample 3D, and FIG. 25D shows an electrondiffraction pattern of Sample 3D. FIG. 25E shows a cross-sectional TEMimage of Sample 3J, and FIG. 25F shows an electron diffraction patternof Sample 3J.

As shown in FIG. 25A, a nanocrystal is observed in Sample 3A bycross-sectional TEM. In addition, as shown in FIG. 25B, the observedelectron diffraction pattern of Sample 3A has a region with highluminance in a circular (ring) pattern. Furthermore, a plurality ofspots can be shown in the ring-shaped region.

As shown in FIG. 25C, a CAAC structure and a nanocrystal are observed inSample 3D by cross-sectional TEM. In addition, as shown in FIG. 25D, theobserved electron diffraction pattern of Sample 3D has a region withhigh luminance in a circular (ring) pattern. Furthermore, a plurality ofspots can be shown in the ring-shaped region. In the diffractionpattern, spots derived from the (009) plane are slightly observed.

In contrast, as shown in FIG. 25E, layered arrangement of a CAACstructure is observed in Sample 3J by cross-sectional TEM. Furthermore,spots derived from the (009) plane are included in the electrondiffraction pattern of Sample 3J in FIG. 25F.

The features observed in the cross-sectional TEM images and theplan-view TEM images are one aspect of a structure of an oxidesemiconductor.

According to the above description, the electron diffraction patterns ofSample 3A and Sample 3D each have a region with high luminance in a ringpattern and a plurality of bright spots appear in the ring-shapedregion. Accordingly, Samples 3A and 3D each exhibit an electrondiffraction pattern of the nc-OS and do not show alignment in the planedirection and the cross-sectional direction. Sample 3D is found to be amixed material of the nc structure and the CAAC structure.

In the electron diffraction pattern of Sample 3J, spots derived from the(009) plane of an InGaZnO₄ crystal are included. Thus, Sample 3J hasc-axis alignment and the c-axes are aligned in the directionsubstantially perpendicular to the formation surface or the top surfaceof Sample 3J.

<Analysis of TEM Image>

This section describes the observation and analysis results of Samples3A, 3D, and 3J with an HAADF-STEM.

The results of image analysis of plan-view TEM images are described. Theplan-view TEM images were obtained with a spherical aberration correctorfunction. The plan-view TEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV, and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

FIG. 26A shows a plan-view TEM image of Sample 3A, and FIG. 26B shows animage obtained through image processing of the plan-view TEM image ofSample 3A. FIG. 26C shows a plan-view TEM image of Sample 3D and FIG.26D shows an image obtained through image processing of the plan-viewTEM image of Sample 3D. FIG. 26E shows a plan-view TEM image of Sample3J and FIG. 26F shows an image obtained through image processing of theplan-view TEM image of Sample 3J.

The images obtained through image processing of the plan-view TEM imagesin FIGS. 26B, 26D, and 26F are images obtained through image analysis ofthe plan-view TEM images in FIGS. 26A, 26C, and 26E by the methoddescribed in Example 1 and applying color in accordance with the angleof the hexagonal lattice. In other words, the images obtained throughthe image processing of the plan-view TEM images are each an image inwhich the orientations of lattice points in certain wavenumber rangesare extracted by color-coding the certain wavenumber ranges andproviding gradation in the ranges in an FFT filtering image of theplan-view TEM image.

As shown in FIGS. 26A to 26F, in Samples 3A and 3D in which nc isobserved, the hexagons are oriented randomly and distributed in a mosaicpattern. In Sample 3J in which a layered structure is observed in thecross-sectional TEM image, regions with uniformly oriented hexagonsexist in a large area of several tens of nanometers. In Sample 3D, it isfound that an nc region in a random mosaic pattern and a large-arearegion with uniformly oriented hexagons as in Sample 3J are included.

It is found from FIGS. 26A to 26F that as the substrate temperature atthe time of formation is lower or the oxygen gas flow rate ratio at thetime of formation is lower, regions in which the hexagons are orientedrandomly and distributed in a mosaic pattern are likely to exist.

Through the analysis of a plan-view TEM image of a CAAC-OS, a boundaryportion where angles of hexagonal lattices change can be examined.

Next, Voronoi diagrams were formed using lattice point groups in Sample3A. The Voronoi diagrams were obtained by the method described inExample 1.

FIGS. 27A to 27C show the proportions of the shapes of Voronoi regions(tetragon, pentagon, hexagon, heptagon, octagon, and enneagon) inSamples 3A, 3D, and 3J, respectively. Bar graphs show the numbers of theshapes of Voronoi regions (tetragon, pentagon, hexagon, heptagon,octagon, and enneagon) in the samples. Furthermore, tables show theproportions of the shapes of Voronoi regions (tetragon, pentagon,hexagon, heptagon, octagon, and enneagon) in the samples.

It is found from FIGS. 27A to 27C that there is a tendency that theproportion of hexagons is high in Sample 3J with a high degree ofcrystallinity and the proportion of hexagons is low in Sample 3A with alow degree of crystallinity. The proportion of hexagons in Sample 3D isbetween those in Samples 3J and 3A. Accordingly, it is found from FIGS.27A to 27C that the crystal state of the oxide semiconductorsignificantly differs under different formation conditions.

It is found from FIGS. 27A to 27C that as the substrate temperature atthe time of formation is lower or the oxygen gas flow rate ratio at thetime of formation is lower, the degree of crystallinity is lower and theproportion of hexagons is lower.

<Elementary Analysis>

This section describes the analysis results of elements included inSample 3A. For the analysis, by energy dispersive X-ray spectroscopy(EDX), EDX mapping images are obtained. An energy dispersive X-rayspectrometer AnalysisStation JED-2300T manufactured by JEOL Ltd. is usedas an elementary analysis apparatus in the EDX measurement. A Si driftdetector is used to detect an X-ray emitted from the sample.

In the EDX measurement, an EDX spectrum of a point is obtained in such amanner that electron beam irradiation is performed on the point in adetection target region of a sample, and the energy of characteristicX-ray of the sample generated by the irradiation and its frequency aremeasured. In this example, peaks of an EDX spectrum of the point wereattributed to electron transition to the L shell in an In atom, electrontransition to the K shell in a Ga atom, and electron transition to the Kshell in a Zn atom and the K shell in an O atom, and the proportions ofthe atoms in the point are calculated. An EDX mapping image indicatingdistributions of proportions of atoms can be obtained through theprocess in an analysis target region of a sample.

FIGS. 28A to 28H show a cross-sectional TEM image, a plan-view TEMimage, and EDX mapping images of Sample 3A. In the EDX mapping images,the proportion of an element is indicated by grayscale: the moremeasured atoms exist in a region, the brighter the region is; the lessmeasured atoms exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIGS. 28B to 28D and 28F to28H is 7,200,000 times.

FIG. 28A shows a cross-sectional TEM image, and FIG. 28E shows aplan-view TEM image. FIG. 28B shows a cross-sectional EDX mapping imageof In atoms, and FIG. 28F shows a plan-view EDX mapping image of Inatoms. In the EDX mapping image in FIG. 28B, the proportion of the Inatoms in all the atoms is 8.64 atomic % to 34.91 atomic %. In the EDXmapping image in FIG. 28F, the proportion of the In atoms in all theatoms is 5.76 atomic % to 34.69 atomic %.

FIG. 28C shows a cross-sectional EDX mapping image of Ga atoms, and FIG.28G shows a plan-view EDX mapping image of Ga atoms. In the EDX mappingimage in FIG. 28C, the proportion of the Ga atoms in all the atoms is2.45 atomic % to 25.22 atomic %. In the EDX mapping image in FIG. 28G,the proportion of the Ga atoms in all the atoms is 1.29 atomic % to27.64 atomic %.

FIG. 28D shows a cross-sectional EDX mapping image of Zn atoms, and FIG.28H shows a plan-view EDX mapping image of Zn atoms. In the EDX mappingimage in FIG. 28D, the proportion of the Zn atoms in all the atoms is5.05 atomic % to 23.47 atomic %. In the EDX mapping image in FIG. 28H,the proportion of the Zn atoms in all the atoms is 3.69 atomic % to27.86 atomic %.

Note that FIGS. 28A to 28D show the same region in the cross section ofSample 3A. FIGS. 28E to 28H show the same region in the plane of Sample3A.

FIGS. 29A to 29C show enlarged cross-sectional EDX mapping images ofSample 3A. FIG. 29A is an enlarged view of a part in FIG. 28B. FIG. 29Bis an enlarged view of a part in FIG. 28C. FIG. 29C is an enlarged viewof a part in FIG. 28D.

The EDX mapping images in FIGS. 29A to 29C show relative distribution ofbright and dark areas, indicating that the atoms have distributions inSample 3A. Areas surrounded by solid lines and areas surrounded bydashed lines in FIGS. 29A to 29C are examined.

As shown in FIG. 29A, a relatively dark region occupies a large area inthe area surrounded by the solid line and a relatively bright regionoccupies a large area in the area surrounded by the dashed line. Asshown in FIG. 29B, a relatively bright region occupies a large area inthe area surrounded by the solid line and a relatively dark regionoccupies a large area in the area surrounded by the dashed line.

That is, it is found that the areas surrounded by the solid lines areregions including a relatively large number of In atoms and the areassurrounded by the dashed lines are regions including a relatively smallnumber of In atoms. FIG. 29C shows that an upper portion of the areasurrounded by the solid line is relatively bright and a lower portionthereof is relatively dark. Thus, it is found that the area surroundedby the solid line is a region including In_(X2)Zn_(Y2)O_(Z2), InO_(X1),or the like as a main component.

It is found that the area surrounded by the solid line is a regionincluding a relatively small number of Ga atoms and the area surroundedby the dashed line is a region including a relatively large number of Gaatoms. As shown in FIG. 29C, a relatively bright region occupies a largearea in a right portion in the area surrounded by the upper dashed lineand a dark region occupies a large area in a left portion therein. Asshown in FIG. 29C, a relatively bright region occupies a large area inan upper left portion in the area surrounded by the lower dashed lineand a dark region occupies a large area in a lower right portiontherein. Thus, it is found that the area surrounded by the dashed lineis a region including GaO_(X3), Ga_(X4)Zn_(Y4)O_(Z4), or the like as amain component.

Furthermore, as shown in FIGS. 29A to 29C, the In atoms are relativelymore uniformly distributed than the Ga atoms, and regions includingInO_(X1) as a main component are seemingly joined to each other througha region including In_(X2)Zn_(Y2)O_(Z2) as a main component. It can bethus guessed that the regions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)as a main component extend like a cloud.

An In—Ga—Zn oxide having a composition in which the regions includingGaO_(X3) as a main component and the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component are unevenlydistributed and mixed can be referred to as CAC-IGZO.

As shown in FIGS. 29A to 29C, each of the regions including GaO_(X3) asa main component and the regions including In_(X2)Zn_(Y2)O_(Z2) orInO_(X1) as a main component has a size of greater than or equal to 0.5nm and less than or equal to 10 nm, or greater than or equal to 1 nm andless than or equal to 3 nm.

As described above, it is confirmed that the CAC-IGZO has a structuredifferent from that of an IGZO compound in which metal elements areevenly distributed, and has characteristics different from those of theIGZO compound. That is, it can be confirmed that in the CAC-IGZO,regions including GaO_(X3) or the like as a main component and regionsincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component areseparated to form a mosaic pattern.

Accordingly, it can be expected that when CAC-IGZO is used for asemiconductor element, the property derived from GaO_(X3) or the likeand the property derived from In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)complement each other, whereby high on-state current (Ion), highfield-effect mobility (μ) and low off-state current (I_(off)) can beachieved. A semiconductor element including CAC-IGZO has highreliability. Thus, CAC-IGZO is suitably used in a variety ofsemiconductor devices typified by a display.

At least part of this example can be implemented in combination with anyof embodiments and the other examples described in this specification asappropriate.

Example 4

In this example, the transistor 150 including the oxide semiconductor108 of one embodiment of the present invention was fabricated andsubjected to tests for electrical characteristics and reliability. Inthis example, nine transistors, i.e., Samples 4A, 4B, 4C, 4D, 4E, 4F,4G, 4H, and 4J, were fabricated as the transistor 150 including theoxide semiconductor 108.

<<Structure of Samples and Fabrication Method Thereof>>

Samples 4A to 4H and 4J relating to one embodiment of the presentinvention are described below. As Samples 4A to 4H and 4J, thetransistors 150 having the structure illustrated in FIGS. 3A to 3C werefabricated by the fabrication method described in Embodiment 2 withreference to FIGS. 6A to 6D, FIGS. 7A to 7C, and FIGS. 8A to 8C.

Samples 4A to 4H and 4J were fabricated at different temperatures anddifferent oxygen flow rate ratios in formation of the oxidesemiconductor 108. The temperatures and the oxygen flow rates information of the oxide semiconductor of Samples 4A to 4H and 4J areshown in Table 4 below.

TABLE 4 Formation conditions of oxide semiconductor film 108 Flow ratePercentage Deposition [sccm] of O₂ temperature O₂ Ar [%] [° C.] Sample4A 30 270 10 R.T. Sample 4B 90 210 30 R.T. Sample 4C 150 150 50 R.T.Sample 4D 30 270 10 130 Sample 4E 90 210 30 130 Sample 4F 150 150 50 130Sample 4G 30 270 10 170 Sample 4H 90 210 30 170 Sample 4J 150 150 50 170

The samples were fabricated by the fabrication method described inEmbodiment 2. The oxide semiconductor 108 was formed using a metal oxidetarget (In:Ga:Zn=1:1:1.2 [atomic ratio]).

The transistor 150 had a channel length of 2 μm and a channel width of 3μm (hereinafter, also referred to as L/W=2/3 μm).

<I_(d)-V_(g) Characteristics of Transistors>

Next, I_(d)-V_(g) characteristics of the transistors (L/W=2/3 μm) inSamples 4A to 4J were measured. As conditions for measuring theI_(d)-V_(g) characteristics of each transistor, a voltage applied to theconductive film 112 serving as a first gate electrode (hereinafter thevoltage is also referred to as gate voltage (V g)) and a voltage appliedto the conductive film 106 serving as a second gate electrode(hereinafter the voltage is also referred to as back gate voltage (V_(b)g)) were changed from −10 V to +10 V in increments of 0.25 V. A voltageapplied to the conductive film 120 a serving as a source electrode (thevoltage is also referred to as source voltage (Vs)) was V (comm), and avoltage applied to the conductive film 120 b serving as a drainelectrode (the voltage is also referred to as drain voltage (V_(d))) was0.1 V and 20 V.

In FIG. 30 , the results of I_(d)-V_(g) characteristics and field-effectmobilities of Samples 4A to 4H and 4J are shown. The solid line and thedashed-dotted line represent I_(d) at V_(d)=20 V and I_(d) at V_(d)=0.1V, respectively. The dashed line represents field-effect mobility. InFIG. 30 , the first vertical axis represents I_(d) [A], the secondvertical axis represents field-effect mobility (μFE) [cm²/Vs], and thehorizontal axis represents V_(g) [V]. The field-effect mobility iscalculated from a value measured at V_(d)=20 V.

As shown in FIG. 30 , the transistors 150 of Samples 4A to 4H and 4Jhave normally-off characteristics. As shown in FIG. 30 , it is foundthat Samples 4A to 4H and 4J have different on-state currents (Ion) anddifferent field effect mobilities, particularly different field effectmobilities in saturation regions. In particular, the maximum saturationmobilities and the rising characteristics of the field-effect mobilitiesaround 0 V differ distinctly.

It is found from FIG. 30 that as the substrate temperature at the timeof formation is lower or the oxygen gas flow rate ratio at the time offormation is lower, the field-effect mobility at low V_(g) issignificantly higher. In particular, Sample 4A has a maximumfield-effect mobility close to 40 cm²/Vs. Having high mobility at lowV_(g) means being suitable for high-speed driving at low voltage;therefore, application to a variety of semiconductor devices typified bya display can be expected.

At least part of this example can be implemented in combination with anyof embodiments and the other examples described in this specification asappropriate.

REFERENCE NUMERALS

001: region, 002: region, 003: region, 100: transistor, 102: substrate,104: insulating film, 106: conductive film, 108: oxide semiconductorfilm, 108 a: oxide semiconductor film, 108 n: region, 110: insulatingfilm, 110_0: insulating film, 112: conductive film, 112_0: conductivefilm, 112_1: conductive film, 112_2: conductive film, 116: insulatingfilm, 118: insulating film, 120 a: conductive film, 120 b: conductivefilm, 122: insulating film, 140: mask, 141 a: opening, 141 b: opening,143: opening, 150: transistor, 160: transistor, 300A: transistor, 300B:transistor, 300C: transistor, 300D: transistor, 302: substrate, 304:conductive film, 306: insulating film, 307: insulating film, 308: oxidesemiconductor film, 312 a: conductive film, 312 b: conductive film, 314:insulating film, 316: insulating film, 318: insulating film, 320 a:conductive film, 320 b: conductive film, 341 a: opening, 341 b: opening,342 a: opening, 342 b: opening, 342 c: opening.

This application is based on Japanese Patent Application Serial No.2016-100939 filed with Japan Patent Office on May 19, 2016, the entirecontents of which are hereby incorporated by reference.

1. A composite oxide semiconductor comprising a plurality of firstregions and a plurality of second regions, wherein the composite oxidesemiconductor is over a substrate, wherein the plurality of firstregions comprise indium, wherein the plurality of second regionscomprise indium, wherein concentrations of indium in the plurality offirst regions are higher than concentrations of indium in the pluralityof second regions, wherein two first regions among the plurality offirst regions are arranged parallel to a top surface of the substrate ina cross-sectional image, wherein two second regions among the pluralityof second regions are arranged parallel to the top surface of thesubstrate in the cross-sectional image, wherein one of the plurality offirst regions is interposed between the two second regions, wherein adiameter of the one of the plurality of first regions is greater than orequal to 0.5 nm and less than or equal to 10 nm in EDX mapping of thecross-sectional image, wherein one of the plurality of second regions isinterposed between the two first regions, and wherein a diameter of theone of the plurality of second regions is greater than or equal to 0.5nm and less than or equal to 10 nm in EDX mapping of the cross-sectionalimage.
 2. A composite oxide semiconductor comprising a plurality offirst regions and a plurality of second regions, wherein the compositeoxide semiconductor is over a substrate, wherein the plurality of firstregions comprise indium, wherein the plurality of second regionscomprise indium, wherein the plurality of first regions comprise moreindium atoms than the plurality of second regions, wherein two firstregions among the plurality of first regions are arranged parallel to atop surface of the substrate in a cross-sectional image, wherein twosecond regions among the plurality of second regions are arrangedparallel to the top surface of the substrate in the cross-sectionalimage, wherein one of the plurality of first regions is interposedbetween the two second regions, wherein a diameter of the one of theplurality of first regions is greater than or equal to 0.5 nm and lessthan or equal to 10 nm in EDX mapping of the cross-sectional image,wherein one of the plurality of second regions is interposed between thetwo first regions, and wherein a diameter of the one of the plurality ofsecond regions is greater than or equal to 0.5 nm and less than or equalto 10 nm in EDX mapping of the cross-sectional image.
 3. The compositeoxide semiconductor according to claim 1, wherein the oxidesemiconductor layer shows a nanobeam electron diffraction pattern with aplurality of bright spots arranged in a ring-like shape.
 4. Thecomposite oxide semiconductor according to claim 2, wherein the oxidesemiconductor layer shows a nanobeam electron diffraction pattern with aplurality of bright spots arranged in a ring-like shape.
 5. Thecomposite oxide semiconductor according to claim 1, wherein theplurality of first regions and the plurality of second regions aredispersed randomly in the oxide semiconductor layer.
 6. The compositeoxide semiconductor according to claim 2, wherein the plurality of firstregions and the plurality of second regions are dispersed randomly inthe oxide semiconductor layer.
 7. A transistor comprising: the compositeoxide semiconductor according to claim 1 in a channel region.
 8. Atransistor comprising: the composite oxide semiconductor according toclaim 2 in a channel region.
 9. A display device comprising: thetransistor according to claim 7 arranged in a pixel.
 10. A displaydevice comprising: the transistor according to claim 8 arranged in apixel.